WO2011079799A1 - Highly active metathesis catalysis selective for romp and rcm - Google Patents

Highly active metathesis catalysis selective for romp and rcm Download PDF

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Publication number
WO2011079799A1
WO2011079799A1 PCT/CN2010/080477 CN2010080477W WO2011079799A1 WO 2011079799 A1 WO2011079799 A1 WO 2011079799A1 CN 2010080477 W CN2010080477 W CN 2010080477W WO 2011079799 A1 WO2011079799 A1 WO 2011079799A1
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Prior art keywords
alkyl
aryl
alkoxy
aryloxy
heterocyclic
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PCT/CN2010/080477
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French (fr)
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Zheng-Yun James Zhan
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Zannan Scitech Co., Ltd.
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Priority to PL16164005T priority Critical patent/PL3064272T3/en
Priority to KR1020127020139A priority patent/KR101509298B1/en
Priority to EP16164005.7A priority patent/EP3064272B1/en
Priority to CA2785864A priority patent/CA2785864C/en
Priority to EP10840586.1A priority patent/EP2519350B1/en
Priority to BR112012016397-3A priority patent/BR112012016397B1/en
Priority to PL10840586T priority patent/PL2519350T3/en
Priority to JP2012546342A priority patent/JP5766717B2/en
Priority to AU2010338707A priority patent/AU2010338707B2/en
Priority to MX2012007758A priority patent/MX338800B/en
Priority to BR122018015766-6A priority patent/BR122018015766B1/en
Priority to ES10840586T priority patent/ES2720898T3/en
Priority to RU2012132191/04A priority patent/RU2546656C2/en
Publication of WO2011079799A1 publication Critical patent/WO2011079799A1/en

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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/58—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present invention relates to novel carbene ligands and their incorporated ruthenium catalysts, which are highly active and selective for different kinds of metathesis reactions such as ROMP and RCM.
  • the invention also relates to preparation of new ruthenium complexes and the use thereof in metathesis, especially effective for preparation of various functional polymers and rubbers.
  • the present invention relates to two classes of novel carbene ligands and their incorporated ruthenium complexes that can be used as highly active metathesis catalysts selective for RCM, CM, and ROMP reactions, respectively.
  • the novel metathesis catalysts are ruthenium complexes with different kinds of new functionally substituted carbene ligands.
  • the new ruthenium complexes of the invention can catalyze different kinds of metathesis reactions in a very effective manner and offer great advantage in activity and selectivity for different kinds of metathesis reactions, especially in ROMP effective for preparation of some functional polymer materials with unique chemical and physical properties.
  • the novel ruthenium complexes of the invention have broad uses in the polymeric and pharmaceutical industries.
  • the present invention provides a kind of compounds to form carbene ligands having the following structure la or lb:
  • n 0 or 1;
  • Y is CH 2 , H, oxygen, nitrogen, carbonyl, imino, Ci-C 2 o alkoxy, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
  • X oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl
  • Y is nitrogen, oxygen, CH, CH 2 , imino, NH, Ci-C 20 alkyl, Ci-C 20 alkoxy, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 3 -C 2 o heteroaryl, Ci-C 2 o alkylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o arylcarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group; "Y— X" is either single bond or double bond;
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 20 alkyl, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 2 -C 20 heterocyclic aryl, Ci-C 20 alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
  • R 1 is H, Ci-C 2 o alkyl, C 2 -C 2 o alkenyl, C 6 -C 2 o aryl, C6-C 20 arylenyl, Ci-C 2 o alkoxy,
  • R 2 is H, Ci-C 2 o alkyl, C 6 -C 2 o aryl, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkyoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o aminocarbonyl, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
  • E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C 2 o alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C 2 -C 2 o alkenyloxy, Ci-C 2 o silanyl, Ci-C 2 o alkylsilyloxy, C 6 -C 2 o aryl, C 6 -C 2 o aryloxy, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, amino, Ci-C 2 o alkylaminocarbonyl, C 6 -C 2 o arylamin
  • n 0 or 1 ;
  • Y is CH 2 , H, oxygen, nitrogen, carbonyl, imino, C 1 -C 15 alkoxy, C 6 -Ci5 aryloxy, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -Cis heterocyclic amino group;
  • X oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl
  • Y is nitrogen, oxygen, CH, CH 2 , imino, NH, C1-C15 alkyl, C1-C15 alkoxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C 3 -Cis heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 arylcarbonyl, C 6 -Ci 5 aryloxycarbonyl, C 1 -C 15 alkylimino, C 1 -C 15 alkylamino, C 6 -Ci 5 arylamino or C 2 -Cis heterocyclic amino group; "Y— X" is either single bond or double bond.
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
  • R 1 is H, C 1 -C15 alkyl, C 2 -Ci 5 alkenyl, C 6 -C15 aryl, C 6 -C15 arylenyl, C 1 -C15 alkoxy, C1-C15 alkylthio, C6-C15 arylthio, C6-C15 aryloxy, C 3 -Ci 5 heteroaryl or C 2 -Ci 5 heterocyclic group;
  • R 2 is H, C 1 -C15 alkyl, C 6 -C15 aryl, C 1 -C15 alkylcarbonyl, C 6 -C15 arylcarbonyl, C 1 -C15 alkyoxycarbonyl, C 6 -C15 aryloxycarbonyl, C 1 -C15 aminocarbonyl, C 3 -Ci 5 heteroaryl or C 2 -Ci 5 heterocyclic group;
  • E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C 1 -C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C 2 -Ci 5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-C15 aryl, C6-C15 aryloxy, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-C15 arylaminocarbonyl, C1-C15 alkylamido, C6-C15 ary
  • n 0 or 1 ;
  • Y is oxygen, nitrogen, carbonyl, imino, Ci-C 8 alkoxy, C 6 -C 8 aryloxy, Ci-C 8 alkoxycarbonyl, C 6 -C 8 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -Ci 2 heterocyclic amino group;
  • X is nitrogen, oxygen, sulfur, CH, CH 2 , carbonyl
  • Y is oxygen, nitrogen, CH, CH 2 , imino, H, C1-C15 alkyl, Ci-C 8 alkoxy, C 6 -Ci5 aryl, C 6 -Ci 2 aryloxy, C 3 -Ci 2 heteroaryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 arylcarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group; "Y— X" is either single bond or double bond.
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
  • R 1 is H, Ci-C 8 alkyl, C 2 -C 8 alkenyl, C6-C 12 aryl or C6-C 12 arylenyl;
  • R 2 is methyl, ethyl, isopropyl, Ci-C 8 alkyl or C 6 -Ci 2 aryl;
  • E, E , E , E J , E , E E° and E' are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminos
  • n 0 or 1;
  • Y is CH 2 , NH, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino or C 6 -C 9 arylamino group;
  • X is nitrogen, C 1 -C 3 alkylamino, CH, CH 2 , or carbonyl;
  • Y is oxygen, nitrogen, imino, NH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, or C 6 -C 9 arylamino;
  • Y— X is either single bond or double bond;
  • X 1 is CH 2 , substituted or unsubstituted phenyl, or carbonyl; Y 1 is oxygen or carbonyl;
  • R 1 is H
  • E is H, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl;
  • E 1 and E 2 are each H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
  • E 4 is H or C 1 -C 4 alkyl
  • E 5 and E 6 is H, halogen, C 1 -C 4 alkyl or Ci-C 6 alkoxy;
  • E 7 is H or C 1 -C 4 alkyl.
  • the present invention provides a kind of transition metal complex having the following structure Ila or lib:
  • n 0 or 1 ;
  • M is a transition metal
  • L 1 and L 2 are the same or different and each selected from halogen anion (CI “ , Br “ or I “ ), RC(0)0 “ or ArO " anion;
  • L is an electron-donating ligand
  • X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl
  • Y is nitrogen, oxygen, CH, CH 2 , imino, Ci-C 20 alkoxy, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 3 -C 20 heteroaryl, Ci-C 2 o alkylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o arylcarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group; "Y— x" is either single bond or double bond;
  • Y is oxygen, nitrogen, carbonyl, imino, Ci-C 2 o alkoxy, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
  • L 3 is an electron-donating ligand
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 2 o alkyl, C 6 -C 2 o aryl, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
  • R 1 is H, Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 6 -C 20 arylenyl, Ci-C 20 alkoxy, Ci-C 2 o alkylthio, C 6 -C 2 o arylthio, C 6 -C 2 o aryloxy, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
  • R 2 is H, Ci-C 2 o alkyl, C 6 -C 2 o aryl, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkyoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o aminocarbonyl, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
  • E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C 2 o alkyl, Ci-C 2 o alkoxy, Ci-C 2 o alkylthio, C 2 -C 2 o alkenyloxy, Ci-C 2 o silanyl, Ci-C 2 o alkylsilyloxy, C 6 -C 2 o aryl, C 6 -C 2 o aryloxy, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, amino, Ci-C 2 o alkylaminocarbonyl, C6-C20 arylamino
  • L is heterocyclic carbene ligand or phosphine P(R 8 ) 2 (R 9 ) having the following structure Ilia, Illb, IIIc, or Hid:
  • R 4 and R 5 are each C1-C20 alkyl, C6-C20 aryl, C1-C20 alkylamido, C6-C20 arylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
  • R 6 and R 7 are each H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C2-C20 heterocyclic, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C 6 -C 20 arylcarbonyl, C 1 -C 20 alkoxycarbonyl, C 6 -C 20 aryloxy carbonyl, amino, C 1 -C 20 alkylaminocarbonyl, C 6 -C 20 arylaminocarbonyl, C 1 -C 20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfony
  • R 8 and R 9 are each C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl or C2-C20 heterocyclic group.
  • R 4 and R 5 each is aryl
  • R 6 and R 7 each is H.
  • M is ruthenium (Ru), wolfram (W) or nickel (Ni);
  • L is Ilia or Hid; wherein q, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 each is as defined above.
  • Y is oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C 6 -Ci5 aryloxy, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -C15 heterocyclic amino group;
  • X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl
  • Y is nitrogen, oxygen, CH, CH 2 , imino, C1-C15 alkoxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 arylcarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -Cis heterocyclic amino group; "Y— x" is either single bond or double bond;
  • L 3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C 2 -Cis alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C1-C15 alkylcarbonyl, C 6 -Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkyla
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , C1-C15 alkyl, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C 2 -Cis heterocyclic aryl, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -Cis heterocyclic amino group.
  • Y is oxygen, nitrogen, carbonyl, imino, Ci-C 8 alkoxy, C 6 -Ci 2 aryloxy, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group;
  • X oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl
  • Y is nitrogen, oxygen, CH, CH 2 , imino, Ci-C 8 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, C 3 -Ci 2 heteroaryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 arylcarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group; "Y— x" is either single bond or double bond;
  • L 3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-Ci 2 alkylaminocarbonyl, C
  • X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 8 alkyl, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, C 2 -Ci 2 heterocyclic aryl, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group;
  • R 1 is H, Ci-C 8 alkyl, C 2 -C 8 alkenyl, C 6 -C 12 aryl or C 6 -C 12 arylenyl;
  • R 2 is methyl, ethyl, isopropyl, Ci-C 8 alkyl or C 6 -Ci 2 aryl;
  • E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylaminosulfonyl, C 6 -Ci
  • M is ruthenium
  • L 1 and L 2 each is chloride anion
  • n 0 or 1;
  • Y is CH 2 , H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group;
  • X is nitrogen, C 1 -C 3 alkylamino, CH, CH 2 , or carbonyl;
  • Y is oxygen, nitrogen, imino, NH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, or C 6 -C 9 arylamino;
  • Y— X is either single bond or double bond;
  • L 3 is one substituted pyridine at the meta-position or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to ruthenium cation, wherein the substituents at the meta-position or para-position of pyridine are each selected from halogen, nitro, C 1 -C 3 alkyl, C 1 -C3 alkoxy, Ci-C 6 alkylamino, unsubstituted or substituted C 6 -Ci 2 aryl;
  • X 1 is CH 2 , substituted or unsubstituted phenyl, or carbonyl; Y 1 is oxygen or carbonyl;
  • R 1 is H
  • E is H, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl;
  • E 1 and E 2 are each H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; E 3 is H;
  • E 4 is H or Ci-C 4 alkyl
  • E 5 and E 6 is H, halogen, Ci-C 4 alkyl or Ci-C 6 alkoxy;
  • E 7 is H or Ci-C 4 alkyl.
  • the third aspect provides the following synthetic methods of making different kinds of transition metal complexes Ila-IIb.
  • the complex ligands Ia-Ib could be prepared by the following S
  • Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 and E 3 each is as defined above.
  • the ligands Ia-Ib can be prepared by the coupling of chemicals SM-la or SM-Ib with vinyl borane reagent in organic solvent such as DMF in the prence of Pd catalyst.
  • SM-la or SM-Ib were ordered by custom synthesis from Zannan Pharma Ltd, in China.
  • the Ru complex 2h is prepared by the reaction of reagent SM-2b and RuCl 2 (PPh 3 ) 3 in anhydrous DCM in a three-neck flask filled with inert gas (Ar).
  • step (2) The Ru complex 2h obtained by step (1) is reacted with complex ligand la or lb to prepare another Ru complex Va or Vb in a flask filled with inert gas (Ar); wherein, Va and Vb are compounds Ila or lib when L is PPh 3 ; M, L 1 , L 2 , Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 and E 3 are each as defined above.
  • L 1 and L 2 each is chloride anion (CI " ).
  • the preferred one of E and X 1 is hydrogen; the preferred usage of anhydrous organic solvent is 5-30 times weight of SM-2; the more preferred usage is 15 times; the preferred reaction temperature is 25-75 ° C, the more preferred temperature is 50-65 ° C .
  • the preferred reaction temperature is -50 ° C to -85 ° C, the more preferred temperature is -60 ° C to -75 ° C ;
  • the preferred usage of ML ⁇ Ls is 0.3-1.0 times molar ratio of SM-2, the more preferred usage is 0.6-0.7 times;
  • the preferred compound of ML 1 !?” is RuCl 2 (PPh 3 ) 3 ;
  • the preferred reaction temperature is -50 ° C to -85 ° C, the more preferred temperature is -60 ° C to -75 ° C ;
  • the preferred usage of complex ligand la or lb is 1-3 molar ratio of complex intermediate, the preferred usage is 1.5-2 eq.
  • the preferred one in structure of transition metal complexs as the product Ila or lib, where a preferred ligand L is Ilia or Hid.
  • the preferred reaction termperature is 20 ° C to 75 ° C, the more preferred reaction temperature reacted with complex ligand Ilia is 60 ° C to 75 ° C, the more preferred reaction temperature reacted with complex ligand Hid is 20 ° C to 35 ° C ;
  • the preferred usage of Ilia or Hid is 1-3 times molar ratio of complex intermediate Va or Vb, the more preferred molar ratio is 1.5-2 eq;
  • the preferred reaction temperature is 20 ° C to 35 ° C .
  • L 1 and L 2 each is chloride anion.
  • the metal complex Ila or lib of the present invention could also be prepared by the following two alternative procedures described in Schemes 2 & 3 :
  • Z is TsNHN in structure la or lb.
  • the present invention provides a method of carrying out a metathesis reaction effectively with olefin substrate, comprising intramolecular ring-closing metathesis (RCM), intermolecular cross metathesis (CM), acyclic diene metathesis (ADMET), or ring-opening metathesis polymerization (ROMP) of cyclo-olefin substrate selectively in the presence of the novel ruthenium catalysts.
  • RCM intramolecular ring-closing metathesis
  • CM intermolecular cross metathesis
  • ADMET acyclic diene metathesis
  • RMP ring-opening metathesis polymerization
  • the preferred cyclo-olefin substrate for ROMP is optionally selected from dicyclopentadiene (DCPD), norbornene, cyclooctene, or a kind of tensional cycloolefin; each is optionally substituted or unsubstituted with one or more of F, CI, Br, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-C15 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C1-C15 alkylcarbonyl, C 6 -Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C 6 -Ci5 arylaminocarbonyl, C 1-
  • a kind of tensional cycloolefin substrates include the following structure Via- Vic:
  • A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C 6 -Ci5 arylamino, C1-C15 alkylaminocarbonyl, C 6 -Ci5 arylaminocarbonyl, C1-C15 alkylamido, C 6 -Ci5 arylamido, or C1-C15 heterocyclic amido group;
  • G is a group of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs; R 10 and R 11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C 6 -Ci5 aryloxy, C 6 -Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C 1 -C 15 alkylcarbonyl, C 1 -C 15 alkyloxycarbonyl, C 6 -Ci 5 aryloxycarbonyl, C 1 -C 15 alkylaminocarbonyl, C 6 -Ci 5 arylaminocarbonyl, C 1 -C 15 alkylamido, C 1 -C 15 alkylsulfonyl, C 1 -C 15 alkylsulfonamido, liquid crystal monomer or modified pro-d
  • Linker is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C 6 -Ci5 aryloxy, C 6 -Ci5 aryl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C 6 -Ci 5 arylaminocarbonyl, Ci-C 15 alkylamido, C 6 -Ci 5 arylamido, C1-C15 alkylsulfonamido, C 6 -Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
  • A is O, S, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 aryloxy, C 1 -C 15 alkylthio, Ci-C 8 alkoxycarbonyl, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, or Ci-C 8 heterocyclic amido group;
  • G is a kind of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs;
  • R 10 and R 11 are each H, halogen, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, Ci-C 8 alkylsilyoxy, C 6 -Ci2 aryloxy, C 6 -Ci2 aryl, C2-Q heterocyclic, C3-C12 heterocyclic aryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkyloxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, Ci-C 8 alkylsulfonyl, Ci-C 8 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
  • Linker is Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, Ci-C 8 alkylsilyoxy, C 6 -Ci 2 aryloxy, C 6 -Ci 2 aryl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylsulfonamido, C 6 -Ci 2 arylsulfonamido, C 3 -C 12 heteroaryl or C 2 -C 8 heterocyclic group.
  • A is O, CH 2 , C 1 -C5 alkyl-amino, C 1 -C5 alkoxy, C 1 -C5 alkylaminocarbonyl or C 1 -C5 heterocyclic amido group;
  • Linker is Ci-C 6 alkyl, C 1 -C5 alkoxy, C 1 -C5 alkylthio, C 1 -C5 alkoxycarbonyl, C 1 -C5 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, C 1 -C5 alkylamido or C 6 -Ci 2 arylamido group;
  • G is a kind of optionally modified prodrug of commercial drug Lipitor having the following structure VHa-VIId:
  • R 10 and R 11 are each H, C 1 -C5 alkoxy, C 6 -Ci 2 aryloxy, C 1 -C5 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, C 1 -C5 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, C 1 -C5 alkylamido, C 6 -Ci 2 arylamido, liquid crystal monomer or modified pro-drug;
  • R 12 is cyclopropyl, Ci-C 6 alkly, C 3 -C6 cycloalkyl, Ci-C 6 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 6 alkylamino, C 6 -Ci 2 arylamino, Ci-C 6 alkylsulfonamido, C 6 -Ci 2 arylsulfonamido, C 3 -Ci 2 heterocyclic aryl or C 2 -C 6 heterocyclic group.
  • the present invention provides a method of making a quality-modified polymer having the following structure Villa- Vlllb in the presence of one or two more mixed ruthenium catalysts;
  • the present invention provides a process of preparing functional polymers Villa- Vlllb in the presence of one or two more mixed catalysts.
  • the present invention provides a method of making a modified nitrile butadiene rubber (NBR) or styrene-butadiene rubber (SBR) by depolymerization in the presence of one or more mixed catalysts of the present invention at 30-100°C.
  • NBR modified nitrile butadiene rubber
  • SBR styrene-butadiene rubber
  • the present invention provides a method of making a depolymerized HNBR (hydrogenated nitrile butadiene rubber) or styrene-butadiene rubber by adding one or more mixed catalysts of the present invention first to carry out depolymerization of NBR, followed by adding hydrogen into the reaction under high pressure for hydrogenation at 60-150°C.
  • HNBR hydrogenated nitrile butadiene rubber
  • styrene-butadiene rubber styrene-butadiene rubber
  • the present invention provides a method of making a hydrogenated nitrile butadiene rubber (HNBR) or styrene-butadiene rubber by adding hydrogen under high pressure first, followed by adding one or more mixed catalysts of claim 5 at 60-150°C.
  • HNBR hydrogenated nitrile butadiene rubber
  • styrene-butadiene rubber by adding hydrogen under high pressure first, followed by adding one or more mixed catalysts of claim 5 at 60-150°C.
  • the present invention provides a use of catalysts of the present invention in depolymerization of a rubber comprising at least one carbon-carbon double bond.
  • the present invention provides a use of catalysts of the present invention in hydrogenation of a rubber comprising at least one carbon-carbon double bond.
  • the present invention also provides a useful method of making functional polymers, comprising reacting one or more monomers in the presence of the novel ruthenium catalysts.
  • the present invention provides a composition of comprising a modified prodrug or functional group G having the following structure IXa-IXc:
  • A, G, "Linker”, R 11 and R 12 each is as defined above.
  • Linker R 10 and R 11 each is as defined above;
  • G is a kind of optionally modified pro-drug of Lipitor having the following structure VHa-VIId:
  • R 12 is cyclopropyl, Ci-C 6 alkly, C 3 -C 6 cycloalkyl, Ci-C 6 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci2 aryloxy, Ci-C 6 alkylamino, C 6 -Ci2 arylamino, Ci-C 6 alkylsulfonamido, C 6 -Ci 2 arylsulfonamido, C 3 -C 12 heterocyclic aryl or C 2 -C 6 heterocyclic group.
  • the present invention relates to two classes of novel carbene ligands and ruthenium complexes as catalysts in uses of carrying out metathesis reactions effectively, e.g., preparation of the high strength and/or stiffness polymer materials, functional polymers linked with small molecule pro-drugs and liquid crystal materials.
  • the present invention provides the following significant achievements: 1.
  • Two classes of novel carbene ligands and ruthenium complexes have been designed and prepared, which has different structure and activity with five or six coordinate bonds, especially for the new Ru complexes with six coordinate bonds to form at least one "Ru-N" coordinate bond from the new developed ligands la or lb.
  • the electronic and steric effect of different substituted ligands on the catalytic activity and stability of various new Ru complexes have been studied, and it is found that some of novel Ru catalysts in the present invention have much better catalytic selectivity and variable physical diversity than Grubbs and Hoveyda catalysts in the ROMP and RCM reactions.
  • the present invention provides several developed methods for preparation of carbene ligands and Ru catalysts at lower cost, and it also provides some efficient methods for preparation of various functional polymer materials with different chemical and physical properties.
  • the present invention provides several developed processes of conducting ROMP reaction with one or two more mixed of novel active Ru catalysts for preparation of the high-strength polymer materials and some functional polymers linked with small molecule pro-drugs and/or liquid crystal materials.
  • Figure 1 Single-crystal X-ray Structure of Ru Catalyst 8m.
  • the present invention comprises two novel classes of carbene ligands and ruthenium complexes as catalysts for metathesis reactions.
  • ruthenium complexes as catalysts for metathesis reactions.
  • different kinds of the complex ligands (3a-3bf, 5a- 5j, 7a-7r, 9a-9j) have been prepared and reacted with the Ru complex 1 to obtain different kinds of new Ru complex (4a-4bf, 6a-6j, 8a-8r, lOa-lOj, lla-llr).
  • Ru catalyst 8m is confirmed by single-crystal X-ray as shown ure 1. According to previously described synthetic methods, various new Ru complexes lOa-lOj have been prepared by the reaction listed in Scheme 7, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
  • Scheme 9 A convenient route for preparation of some Ru complexes
  • the starting material 4-SM was reacted with sodium ethoxide to produce carbene intermediate 4-1 first, followed by reacting with RuCl 2 (PPh 3 ) 3 directly to form Ru complex intermediate 4-2.
  • the triphenylphosphine ligand (PPh 3 ) of Ru intermediate 4-2 was replaced by another ligand PCy 3 (4-3, Hid) to form a new Ru complex 4i.
  • the phosphine ligand of Ru intermediate 4-2 or 4i was further replaced by an NHC ligand (H 2 IMes, 4-4, Ilia) to form another Ru complex 4j .
  • the Ru complex 4j could directly react with another ligand 4-chloro pyridine (4-5) to make the Ru complex llh.
  • Ru complex 2h is prepared by the reaction of reagents SM-2b and RuCl 2 (PPh 3 )3 in anhydrous DCM in a three-neck flask filled with inert gas (Ar), followed by reacting the Ru complex 2h with complex ligand 3x (la) to form another Ru complex 2j (Va) in a flask filled with inert gas (Ar).
  • the triphenylphosphine ligand (PPh 3 ) of Ru intermediate 2j was replaced by another phosphine ligand PCy 3 (4-3, Hid) to form a new Ru complex 4x.
  • the phosphine ligand of Ru intermediate 2j or 4x was further replaced by another HC ligand (H 2 IMes, 4-4, Ilia) to form another Ru complex 4aa.
  • Ru complexes 4a-4bj only some of new complexes (such as 4f, 4g, 4u, 4ab, 4aj, 4bb and 4be) show high catalytic activity, the rest of them not listed in Table 1-1 have lower or very poor activities for RCM reaction. Based on the determined results in Table 1-1, the activity of Ru complexes 4a-4bj for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 3a-3bj. However, some of complexes 4a-4bj non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
  • complexes 8a-8u only a few complexes (such as 8b, 8h and 8r) show good activity and much better than the reported catalyst 2c, the rest of them not listed in Table 1-3 have worse or very poor activities.
  • the activity of Ru complexes 8a-8u for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 7a-7u.
  • some of non-active complexes 8a-8u for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
  • complexes lOa-lOj Among complexes lOa-lOj, several complexes (such as 10c, lOd, lOe and lOg) show good or high catalytic activity and much better than the known catalyst 2d, the rest of them not listed in Table 1-4 have worse or very poor activities. Based on the determined results in Table 1-4, the activity of Ru complexes lOa-lOj for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 9a-9j. However, some of non-active complexes 10a- lOj for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
  • Equation 5 (0.1% molar)
  • the ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 8b and 8h of the present invention have better activity and selectivity for norbornene (23) polymerization.
  • Catalytic polymerization was completed in 10-60 min, and the polymer product (24) has better tensile-strength when it is prepared as film.
  • the ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 4ag, 4ar, 4au, 8a, 8b, 8c, 8h, 8m and 8q of the present invention have better activity and selectivity for DCPD (25) polymerization.
  • the ROMP polymerization was completed in 5-60 min for different Ru catalysts.
  • the reaction temperature is preferred to be 40-60 ° C .
  • results of Table 3 show that, small molecule liquid crystal or pro-drug monomer can react with new Ru catalysts selected from the present invention to form polymerized macromolecule liquid crystal (28c and 28d) and polymer-linked prodrugs (28e, 28f and 28g) with special properties and applications.
  • the results of activity test show that several new catalysts (such as 4d, 4f, 6g and 11a) of the present invention have better catalytic activity for olefin monomers (27a-27g), and the ROMP reactions were completed in 5-15 hrs. Yield is better than 80% with optimized polymerization conditions in the presence of new Ru catalyst 4d.
  • the catalysts of the present invention can be used for depolymerization of a rubber comprising at least one carbon-carbon double bond.
  • the depolymerization is conducted by metathesis reaction of carbon-carbon double bond in the rubber in the presence of one or more of catalysts of the present invention.
  • the depolymerized rubber has lower molecular weight and lower mooney viscosity, which can be better used at lower temperature as lower as -40°C.
  • the catalysts of the present invention can be used in hydrogenation of a rubber comprising at least one carbon-carbon double bond.
  • the carbon-carbon double bond in the rubber is hydrogenated under high pressure of hydrogen in the presence of one or more of catalysts of the present invention.
  • the hydrogenated rubber is obtained and could be used as more stable and higher strength rubber.
  • the rubber comprising at least one carbon-carbon double bond can be depolymerized, and followed by hydrogenation under high pressure of hydrogen to produce a lower molecular weight and lower mooney viscosity rubber in the presence of one or more catalysts of the present invention, which can be used at lower temperature as lower as -55°C.
  • the rubber comprising at least one carbon-carbon double bond can be hydrogenated under high pressure of hydrogen and depolymerized simultaneously in the presence of one or more catalysts of the present invention, which can be used at lower temperature as lower as -55°C.
  • the representative examples of rubbers include but not limited to nitrile butadiene rubber, polybutadiene rubber, styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS) or any rubber containing carbon-carbon double bond.
  • SBR styrene-butadiene rubber
  • SBS styrene-butadiene-styrene
  • the BR is depolymerized by using catalyst 4ab at 30 ° C-100 ° C as shown in Equation 10:, and the physical properties of depolymerized NBR are listed in Table 6.
  • Mw molecular weight
  • Mooney viscosity of various nitrile butadiene rubber e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850
  • catalysts of the present invention e.g., catalyst 4ab selected from 4a-4bj, 6a-6j, 8g-8u, lOe-lOg.
  • Equation 11 q > (t + u).
  • Equation 11 The process for Equation 11 was carried out by adding Ru metathesis catalyst (4aa) for depolymerization first at 60 ° C-150 ° C, followed by adding hydrogen under high pressure 2.0-15MPa for hydrogenation in chlorobenzene. It is determined that the molecular weight (Mw) and Mooney viscosity of various nitrile butadiene rubbers (e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850) are significantly reduced down about 30-70%) as needed by depolymerization in chlorobenzene or chloroform in the presence of the catalysts of the present invention (e.g., 4a-4bj, 8g-8u, lOe-lOg), and the hydrogenation degree is determined to be between 90-99.5%) as needed.
  • the depolymerization and hydrogenation results are listed in the following Table 7.
  • Equation 12 Raw Material, which is undepolymerized and unhydrogenated. Equation 12:
  • H 2 C-CH 2 -CH 2 -CH 2 -7- H 2 C-CH CH-CH 2 -)-r ⁇ cH 2 -CH -fcH 2 -CH -
  • Equation 12 q > (t'+u').
  • Equation 12 The process for Equation 12 was carried out by adding hydrogen under high pressure 2.0-15MPa first, followed by adding Ru metathesis catalyst (4aa) to conduct hydrogenation and depolymerization simultaneously in chlorobenzene at 60 ° C-150 ° C . It is determined that the hydrogenation degree is determined to be between 90-99.5% as needed (determined by IHNMR), and the molecular weight (Mw) and Mooney viscosity of various nitrile butadiene rubbers (e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850) are reduced down about 10-50% as needed by depolymerization in chlorobenzene or chloroform in the presence of catalysts (e.g., 4a-4bj, 8g-8u, lOe-lOg). The depolymerization and hydrogenation results are listed in Table 8.
  • RM Raw Material, which is undepolymerized and unhydrogenated.
  • Mw molecular weight
  • Mooney viscosity of various NBR brands (e.g., N41, DN3335, DN3350, and DN2850) are obviously reduced about 30-70% as needed by metathesis depolymerization and hydrogenation by adding hydrogen in chlorobenzene or chloroform in the presence of the Ru catalysts (e.g., 4a-4bj, 8g-8u, lOe-lOg) to obtain different kinds of HNBR products as needed with lower molecular weight (Mooney viscosity range: 20-100MU) and high hydrogenation degree (90-99.5%).
  • Ru catalysts e.g., 4a-4bj, 8g-8u, lOe-lOg
  • the depolymerized NBR can be used in lower temperature as lower as -40 ° C
  • the depolymerized and hydrogenated NBR HNBR
  • the depolymerized and hydrogenated NBR can be used in a temperature as lower as -55 ° C with an improved strength and a better UV-resistance.
  • the present invention provides some useful methods of carrying out ROMP, RCM, CM, and ADMET reactions with one or two more mixed of novel active Ru catalysts for preparation of some functional polymers, lower molecular weight rubbers and/or pharmaceutical intermediates, respectively.
  • THF and Et 2 0 were distilled from sodium metal dried flask, DCM, pentane, and hexanes were distilled from calcium hydride.
  • Different substituted 2-alkoxystyrene ligands were prepared according to literature procedures as shown in Schemes 1-3.
  • SM-Ia and SM-Ib chemicals were obtained from commercial sources or ordered by custom synthesis from Zannan Pharma Ltd., China. General procedures for preparation of different Ru complexes are described in examples 1 and 2, respectively.
  • General procedures for evaluation of the RCM and ROMP reactions are described in examples 104-107, respectively.
  • SM-3a (5.0mmol) was added into a 50 mL of three-neck round-bottom flask filled with inert gas (Ar), and followed by adding DME (10 mL) and deionized water (3 mL). K2CO3 (1.5 eq) was added and the solution was N 2 protected. The reaction was heated to 85 ° C , 2,4,6-Trivinyl-cyclotriboroxane pyridine complex (0.5 eq) and Pd(PPh 3 ) 4 (2%) were added until completed overnight, (monitored by TLC).
  • reaction mixture was filtered and extracted by DCM twice, then purified by flash column eluting with a gradient solvent (PE/EA 400/1 to 100/1) and dried under vacuum to obtain 0.9g of yellow oil products 3a (yield: 86%).
  • the product was confirmed by 1 HNMR.
  • ligand 3e is the same as 3d for preparation of Ru complex 4e, just another Ru complex reagent la was used instead of Ru reagent lb.
  • ligand 3w is the same as 3v for preparation of Ru complex 4w, just another Ru complex reagent la was used instead of Ru reagent lb.
  • ligand 3z is the same as 3y for preparation of Ru complex 4z, just another Ru complex intermediate la was used instead of Ru intermediate lb.
  • ligand 3aa is the same as 3x for preparation of Ru complex 4aa, just another Ru complex intermediate lb was used instead of Ru intermediate la.
  • ligand 3aw is the same as 3av for preparation of Ru complex 4aw, just another Ru complex reagent la was used instead of Ru reagent lb.
  • Ligand 3ba 1H MR (CDC1 3 , 400 MHz): ⁇ 7.23 (m, 4H), 6.92 (m, 2H), 6.80 (m, 1H), 6.67 (m, 2H), 5.68 (d, 1H), 5.39 (d, 1H), 4.64 (s, 2H), 4.06 (s, 2H), 3.75 (s, 3H).
  • the procedure for preparation of Ru complex 4ba is the same as in Example 1 in 1.0 mmol scale. 176 mg of green solid product 4ba was obtained (yield: 22%).
  • Ligand 3bb 1H MR (CDC1 3 , 400 MHz): ⁇ 7.21 (m, 4H), 6.90 (m, 2H), 6.78 (m, IH), 6.67 (d, 2H), 5.68 (d, IH), 5.38 (d, IH), 5.06 (m, IH), 4.64 (s, 2H), 3.99 (s, 2H), 1.23 (d, 6H).
  • Ligand 3bc 1H MR (CDCI 3 , 400 MHz): ⁇ 7.23 (m, 2H), 6.92 (m, 2H), 6.81 (m, 2H), 6.67 (m, 2H), 5.67 (d, 1H), 5.37 (d, 1H), 5.05 (m, 1H), 4.57 (s, 2H), 3.98 (s, 2H), 3.77 (s, 3H), 1.22 (d, 6H).
  • Ligand 3bd 1H MR (CDC1 3 , 400 MHz): ⁇ 7.21 (m, 2H), 7.16 (m, 2H ), 6.86 (m, 2H), 6.58 (m, 2H), 5.68 (d, 1H), 5.39 (d, 1H), 5.06 (m, 1H), 4.60 (s, 2H), 3.97 (s, 2H), 1.23 (d, 6H).
  • Ligand 3be H MR (CDC1 3 , 400 MHz): ⁇ 7.23 (m, 2H), 6.91 (m, 4H), 6.61 (m, 2H), 5.68 (d, 1H), 5.38 (d, 1H), 5.05 (m, 1H), 4.58 (s, 2H), 3.95 (s, 2H), 1.23 (d, 6H).
  • Ligand 3bj 1H MR (CDC1 3 , 400 MHz): ⁇ 7.58-7.57 (d, IH), 7.38-7.36 (d, IH), 7.32-7.25 (m, 2H), 7.08-7.00 (m, 3H), 6.74-6.70 (m, IH), 6.65-6.63 (d, IH), 5.73-5.69 (m, IH), 5.33-5.30 (m, IH), 4.90 (s, IH), 4.35 (s, 2H), 2.63 (s, 6H).
  • SMl-5a (5.0mmol) and SM2-5a (5.0mmol) was added into a 50 mL of three-neck round-bottom flask filled with inert gas (Ar), and followed by adding anhydrous DCM (10 mL) and Na 2 S0 4 (5 eq) was added. The reaction was stirred until completed overnight (monitored by TLC). The reaction mixture was filtered, and the crude imine product 5a (1.25g, 97%) was obtained by removing all DCM solvent under vacuum. The crude imine product 5a was directly used for next step to prepare Ru complex 6a.
  • Ru complex (6d): 1 HNMR (400 MHz, CDC1 3 ): ⁇ 18.73 (s, 1H, Ru CH), 8.62 (s, 1H), 7.67-7.46 (m, 3H), 7.11 (s, 4H), 6.78-6.65 (m, 5H), 4.13 (s, 4H, NCH 2 CH 2 N), 3.81 (s, 3H), 2.49 (m, 18H).
  • the product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 8d could be directly used for metathesis reaction.
  • the product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 8e could be directly used for metathesis reaction.
  • Ligand 7p 1H- MR 400 MHz, CDC13: ⁇ 7.42 (m, 1H), 7.17-7.15 (m, 1H), 7.09-7.06 (m, 1H), 7.04-6.98 (m, 1H), 5.69-5.65 (m, 1H), 5.30-5.27 (m, 1H), 5.0-4.95 (m, 1H), 3.75 (s, 2H), 3.23-3.19 (m, 2H), 1.19-1.18 (d, 6H), 1.07-1.04 (m, 3H).
  • Example 1 in 1.0 mmol scale. 386 mg of brown solid product 8r was obtained by precipitation in hexane and MeOH, and the crude product 8r is unstable and difficult to detect the structure by 1 HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction.
  • Example 81
  • the Ru complex (Grela catalyst 2f, l .Ommol) and 4-chlorin pyridine ligand (lOmmol) were reacted directly to form another Ru complex 11a in 20 mL of anhydrous DCM in a 100 mL of three-neck flask filled with inert gas (Ar), and the reaction mixture was stirred for 0.5 hr at room temperature. After complete, 20mL of pentane (-10 ° C) was added into reaction solution, then filtered and washed with MeOH to obtain 747 mg of yellow-green solid product 11a, yield: 95%.

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Abstract

A kind of novel carbene ligand and corresponding novel ruthenium catalyst are provided. The ruthenium catalysts are highly active and selective for ROMP and RCM reactions. The significant electronic effects of different substituted carbene ligands on the catalytic activity and stability of corresponding carbene ruthenium complexes are disclosed. The methods for preparing new ruthenium complexes are disclosed. Moreover, efficient methods for making various functional polymers and quality modified nitrile butadiene rubbers via different metathesis and hydrogenation reactions in the presence of the new ruthenium catalysts are provided.

Description

HIGHLY ACTIVE METATHESIS CATALYSTS SELECTIVE FOR ROMP
AND RCM REACTIONS
FIELD OF THE INVENTION
The present invention relates to novel carbene ligands and their incorporated ruthenium catalysts, which are highly active and selective for different kinds of metathesis reactions such as ROMP and RCM. The invention also relates to preparation of new ruthenium complexes and the use thereof in metathesis, especially effective for preparation of various functional polymers and rubbers.
BACKGROUND OF THE INVENTION
Since Richard R. Schrock and Robert H. Grubbs prepared two kinds of metathesis catalysts with transition metal carbene structure in the 1990's, it has been drawning extensive attention in the development of more active and selective ruthenium catalysts for different kinds of olefin metathesis reactions, e.g., ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), and cross metathesis (CM).
So far, some useful ruthenium complexes have been reported as active metathesis catalysts (la-lb and 2a-2f in Scheme 1) for RCM and ROMP reactions (Grubbs et al, J. Am. Chem. Soc. 1992, 114, 3974-3975, Org. Lett. 1999, 1, 953-956, WO2007081987A1 ; Hoveyda et al, J. Am. Chem. Soc. 1999, 121, 791-799, J. Am. Chem. Soc. 2000, 122, 8168-8179; Yamaguchi et al, Chem. Commun. 1998, 1399-1400; Zhan et al, US20070043180A1, WO 2007003135A1; Grela et al, WO2004035596A1 ; Slugovc et al, Organometallics 2004, 23(15), 3623-3626 for catalyst 2d; and Organometallics 2005, 24(10), 2255-2258 for catalyst 2e). However, a disadvantage of all reported ruthenium catalysts is obviously substrate-dependent for different kinds of ruthenium catalysts in metathesis reactions, and it is still very difficult to find some active metathesis catalysts selective for RCM and ROMP reactions, respectively. Moreover, only a few metathesis catalysts could be used effectively to make high-strength and high-stiffness polydicyclopentadiene (PDCPD) material by ROMP reaction.
Figure imgf000003_0001
la lb 2a 2b
Grubbs Catalyst (1st) Grubbs Catalyst (2nd) Hoveyda Catalyst Zhan Catalyst
Figure imgf000003_0002
2c 2d 2e 2f (Grela Catalyst)
Scheme 1 Structure of Some Active Catalysts for ROMP and RCM Reaction Currently ROMP reaction is broadly used for preparation of various high-strength and other functional polymers. To overcome the activity and selectivity problems for ROMP catalysts, it has become a goal to develop more active and selective metathesis catalysts as an alternative for ROMP and RCM reactions, especially in ROMP for effective preparation and modification of different functional polymer materials. It is significantly important to develop more active and selective ruthenium catalyst for ROMP reactions with different kinds of olefin substrates to prepare highly functional polymer materials and also to improve polymer properties.
SUMMARY OF THE INVENTION
The present invention relates to two classes of novel carbene ligands and their incorporated ruthenium complexes that can be used as highly active metathesis catalysts selective for RCM, CM, and ROMP reactions, respectively. The novel metathesis catalysts are ruthenium complexes with different kinds of new functionally substituted carbene ligands. The new ruthenium complexes of the invention can catalyze different kinds of metathesis reactions in a very effective manner and offer great advantage in activity and selectivity for different kinds of metathesis reactions, especially in ROMP effective for preparation of some functional polymer materials with unique chemical and physical properties. The novel ruthenium complexes of the invention have broad uses in the polymeric and pharmaceutical industries.
In the first aspect, the present invention provides a kind of compounds to form carbene ligands having the following structure la or lb:
Figure imgf000004_0001
la lb
Wherein Z is CH2= or Ts HN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, Ci-C20 alkyl, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C2o heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— X" is either single bond or double bond;
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C20 alkyl, C6-C20 aryl, C6-C20 aryloxy, C2-C20 heterocyclic aryl, Ci-C20 alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
R1 is H, Ci-C2o alkyl, C2-C2o alkenyl, C6-C2o aryl, C6-C20 arylenyl, Ci-C2o alkoxy,
Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group;
R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C2o arylaminocarbonyl, Ci-C2o alkylamido, C6-C2o arylamido, Ci-C2o alkylaminosulfonyl, C6-C2o arylamino sulfonyl, Ci-C2o sulfonylamido, C3-C2o heteroaryl or C2-C2o heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group;
In one preferred embodiment in the present invention, the formula Ia-Ib,
Z is CH2 or Ts HN=;
m = 0 or 1, n = 0 or 1 ;
When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, C1-C15 alkyl, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-Cis heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group;
R1 is H, C1-C15 alkyl, C2-Ci5 alkenyl, C6-C15 aryl, C6-C15 arylenyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C15 arylthio, C6-C15 aryloxy, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group;
R2 is H, C1-C15 alkyl, C6-C15 aryl, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkyoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 aminocarbonyl, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Ci5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-C15 aryl, C6-C15 aryloxy, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-C15 arylaminocarbonyl, C1-C15 alkylamido, C6-C15 arylamido, C1-C15 alkylaminosulfonyl, C6-C15 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Ci5 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In one more preferred embodiment in the present invention, in the formula Ia-Ib,
Z is CH2= or Ts HN=;
m = 0 or 1, n = 0 or 1 ;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-C8 aryloxy, Ci-C8 alkoxycarbonyl, C6-C8 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-Ci2 heterocyclic amino group;
When m = 1, X is nitrogen, oxygen, sulfur, CH, CH2, carbonyl; Y is oxygen, nitrogen, CH, CH2, imino, H, C1-C15 alkyl, Ci-C8 alkoxy, C6-Ci5 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
CH2, Ci-C8 alkyl, C6-C8 aryl, C6-C8 aryloxy, C2-C8 heterocyclic aryl, Ci-C8 alkylamino, C6-C8 arylamino or C2-C8 heterocyclic amino group;
R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl;
R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl;
1 2 3 4 5 6 7
E, E , E , EJ, E , E E° and E' are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In one most preferred embodiment in the present invention, the formula Ia-Ib Z is CH2= or Ts HN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH2, NH, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group;
When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond;
When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl;
R1 is H;
when n = 1, R2 is methyl, ethyl, or isopropyl; and when n = 0, R2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure la.
E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl;
E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
E3 is H;
E4 is H or C1-C4 alkyl;
E5 and E6 is H, halogen, C1-C4 alkyl or Ci-C6 alkoxy;
E7 is H or C1-C4 alkyl.
In the second aspect, the present invention provides a kind of transition metal complex having the following structure Ila or lib:
Figure imgf000007_0001
Wherein: m = 0 or 1, and n = 0 or 1 ;
When n = 0; p = 0 or 1 ; when n = 1, p = 0;
M is a transition metal;
L1 and L2 are the same or different and each selected from halogen anion (CI", Br" or I"), RC(0)0" or ArO" anion;
L is an electron-donating ligand;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— x" is either single bond or double bond;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
When n = 0 and p = 1, L3 is an electron-donating ligand;
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C2o alkyl, C6-C2o aryl, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
R1 is H, Ci-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C6-C20 arylenyl, Ci-C20 alkoxy, Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group;
R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, Ci-C2o alkoxy, Ci-C2o alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In preferred embodiment Ila or lib, L is heterocyclic carbene ligand or phosphine P(R8)2(R9) having the following structure Ilia, Illb, IIIc, or Hid:
R4 D 8
Figure imgf000009_0001
Ilia Illb IIIc Hid
Wherein, q = 1, 2 or 3;
R4 and R5 are each C1-C20 alkyl, C6-C20 aryl, C1-C20 alkylamido, C6-C20 arylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R6 and R7 are each H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C2-C20 heterocyclic, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxy carbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R8 and R9 are each C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl or C2-C20 heterocyclic group.
In one preferred embodiment, wherein L is formula Ilia or Hid; and in Ilia, q =
1 or 2, R4 and R5 each is aryl, R6 and R7 each is H.
In one more preferred embodiment, wherein L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy).
In another preferred embodiment, in Ila-IIb,
M is ruthenium (Ru), wolfram (W) or nickel (Ni);
m = 0 or 1, n = 0 or 1; L1 and L2 each is chloride (CI");
L is Ilia or Hid; wherein q, R1, R2, R4, R5, R6, R7, R8, R9, E, E1, E2, E3, E4, E5, E6 and E7 each is as defined above.
When n = 0, p = 0 or 1; when n = 1, p = 0;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-C15 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— x" is either single bond or double bond;
When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Cis alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylamino sulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Cis heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group.
In one more preferred embodiment of the present invention, wherein the structure Ila or lib: When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-Ci2 aryloxy, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C8 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— x" is either single bond or double bond;
When n = 0, p = 0 or 1; when n = 1, p = 0;
When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-Ci2 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylamino sulfonyl, Ci-C8 sulfonylamido, C3-Ci2 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group;
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C8 alkyl, C6-Ci2 aryl, C6-Ci2 aryloxy, C2-Ci2 heterocyclic aryl, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group;
R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl;
R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-Q heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group..
In one most preferred embodiment of the present invention, wherein the structure
Ila or lib:
M is ruthenium;
L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy).
L1 and L2 each is chloride anion;
m = 0 or 1, and n = 0 or 1;
When m = 0, Y is CH2, H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group;
When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond;
When n = 0, p = 0 or 1; when n = 1, p = 0.
When n = 0 and p = 1 , L3 is one substituted pyridine at the meta-position or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to ruthenium cation, wherein the substituents at the meta-position or para-position of pyridine are each selected from halogen, nitro, C1-C3 alkyl, C1-C3 alkoxy, Ci-C6 alkylamino, unsubstituted or substituted C6-Ci2 aryl;
When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl;
R1 is H;
when n = 1, R2 is methyl, ethyl, or isopropyl; when n = 0, R2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure Ila.
E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl;
E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy; E3 is H;
E4 is H or Ci-C4 alkyl;
E5 and E6 is H, halogen, Ci-C4 alkyl or Ci-C6 alkoxy;
E7 is H or Ci-C4 alkyl.
The third aspect, the present invention provides the following synthetic methods of making different kinds of transition metal complexes Ila-IIb.
First of all, in the present invention, when Z is CH2, the complex ligands Ia-Ib could be prepared by the following S
Figure imgf000013_0001
(Suzuki React ion)
SM-Ib lb
Wherein Y, Y1, R1, R2, E, E1, E2 and E3 each is as defined above.
The ligands Ia-Ib can be prepared by the coupling of chemicals SM-la or SM-Ib with vinyl borane reagent in organic solvent such as DMF in the prence of Pd catalyst. SM-la or SM-Ib were ordered by custom synthesis from Zannan Pharma Ltd, in China.
Method 1 in the following Scheme 1 :
Figure imgf000013_0002
SM-2b
2h
Complex
(Z = CH2) intermediate
(Va or Vb) The intermediate of transition metal complex (Va or Vb) having the following structure:
Figure imgf000014_0001
Va
(1) The Ru complex 2h is prepared by the reaction of reagent SM-2b and RuCl2(PPh3)3 in anhydrous DCM in a three-neck flask filled with inert gas (Ar).
(2) The Ru complex 2h obtained by step (1) is reacted with complex ligand la or lb to prepare another Ru complex Va or Vb in a flask filled with inert gas (Ar); wherein, Va and Vb are compounds Ila or lib when L is PPh3; M, L1, L2, Y, Y1, R1, R2, E, E1, E2 and E3 are each as defined above.
More preferred, L1 and L2 each is chloride anion (CI").
Wherein, in step (1), the preferred one of E and X1 is hydrogen; the preferred usage of anhydrous organic solvent is 5-30 times weight of SM-2; the more preferred usage is 15 times; the preferred reaction temperature is 25-75 °C, the more preferred temperature is 50-65 °C .
In step (2), the preferred reaction temperature is -50 °C to -85 °C, the more preferred temperature is -60 °C to -75 °C ; the preferred usage of ML^Ls is 0.3-1.0 times molar ratio of SM-2, the more preferred usage is 0.6-0.7 times; the preferred compound of ML1!?! is RuCl2(PPh3)3;
In step (3) of method 1, the preferred reaction temperature is -50 °C to -85 °C, the more preferred temperature is -60 °C to -75 °C ; the preferred usage of complex ligand la or lb is 1-3 molar ratio of complex intermediate, the preferred usage is 1.5-2 eq.
When ML!L2L is RuCl2(PPh3)3, the structure of product Va or Vb is as follows:
Figure imgf000015_0001
Va Vb
Method 2: the complex Va or Vb obtained by method 1 is reacted respectively with any electron-donating complex ligand L except PPh3 to prepare following metal complexes Ila or lib, wherein, p = 0, q = 1, definition of M, L, L1, L2, Y, Y1, R1, R2, E, E1, E2 and E3 each is as defined above;
Figure imgf000015_0002
Ila lib
Wherein, the preferred one, in structure of transition metal complexs as the product Ila or lib, where a preferred ligand L is Ilia or Hid. The preferred reaction termperature is 20 °C to 75 °C, the more preferred reaction temperature reacted with complex ligand Ilia is 60 °C to 75 °C, the more preferred reaction temperature reacted with complex ligand Hid is 20 °C to 35 °C ; The preferred usage of Ilia or Hid is 1-3 times molar ratio of complex intermediate Va or Vb, the more preferred molar ratio is 1.5-2 eq;
Method 3: when L is PCy3 or PPh3, the Ila or lib is reacted respectively with any electron-donating complex ligand L (Ilia) or L3 to prepare the metal complex Ila or lib, wherein p = 0, M, L1, L2, Y, Y1, R1, R2, E, E1, E2, E3 is each as defined above.
Method 4: when L is PCy3 or Ilia, the Ila or lib is reacted respectively with any electron-donating complex ligand L3 to prepare the metal complex Ila or lib, wherein p = 1, M, L1, L2, Y, Y1, R1, R2, E, E1, E2, E3 is each as defined above. In method 4, the preferred reaction temperature is 20 °C to 35 °C .
From method 1 to method 4, L1 and L2 each is chloride anion. Based on currently developed technology, the metal complex Ila or lib of the present invention could also be prepared by the following two alternative procedures described in Schemes 2 & 3 :
Scheme 2:
1) NaOEt, EtOH
la or lb Va or Vb
(Z = TsNHN)
Figure imgf000016_0001
Ila or Hb Ila or lib
(L = PCy3) I \
L = Mes-N N-Mes
T
(Mes = 2,4,6-trimethylphenyl)
In the above procedure, Z is TsNHN in structure la or lb.
In Scheme 2, la or lb reacts with NaOEt in anhydrous EtOH to form carbene in a flask filled with inert gas, followed by reacting with RuCl2P(Ph3)3 to form complex Va or Vb. The complex Va or Vb is reacted with Ilia or Hid effectively to obtain the complex Ila or lib in inert gas, respectively.
Scheme 3 :
Figure imgf000016_0002
CuCl, DCM
ΓΛ
(L = PCy3 or Mes-N N-Mes )
T
Complexes Ila and lib could also be prepared by other two alternative synthetic routes as shown in Scheme 3. In Scheme 3, la or lb reacts with ruthenium complex 1 or 2 directly to form the desired complex Ila or lib in a flask filled with inert gas (Ar), respectively.
In the fourth aspect, the present invention provides a method of carrying out a metathesis reaction effectively with olefin substrate, comprising intramolecular ring-closing metathesis (RCM), intermolecular cross metathesis (CM), acyclic diene metathesis (ADMET), or ring-opening metathesis polymerization (ROMP) of cyclo-olefin substrate selectively in the presence of the novel ruthenium catalysts.
The preferred cyclo-olefin substrate for ROMP is optionally selected from dicyclopentadiene (DCPD), norbornene, cyclooctene, or a kind of tensional cycloolefin; each is optionally substituted or unsubstituted with one or more of F, CI, Br, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-C15 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C 1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylaminosulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
In one preferred embodiment of the present invention, wherein a kind of tensional cycloolefin substrates include the following structure Via- Vic:
Figure imgf000017_0001
Via VIb Vic
Wherein r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, or C1-C15 heterocyclic amido group;
G is a group of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs; R10 and R11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C1-C15 alkylcarbonyl, C1-C15 alkyloxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C1-C15 alkylsulfonyl, C1-C15 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, Ci-C 15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
In one more preferred embodiment of the present invention, wherein in structure Vla-VIc:
Wherein r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;:
A is O, S, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 aryloxy, C1-C15 alkylthio, Ci-C8 alkoxycarbonyl, Ci-C8 alkylamino, C6-Ci2 arylamino, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, or Ci-C8 heterocyclic amido group;
G is a kind of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs;
R10 and R11 are each H, halogen, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, C2-Q heterocyclic, C3-C12 heterocyclic aryl, Ci-C8 alkylcarbonyl, Ci-C8 alkyloxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, Ci-C8 alkylsulfonyl, Ci-C8 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heteroaryl or C2-C8 heterocyclic group.
In one most preferred embodiment of the present invention, wherein in structure Vla-VIc:
r = 1 or 2; s = lor 2;
A is O, CH2, C1-C5 alkyl-amino, C1-C5 alkoxy, C1-C5 alkylaminocarbonyl or C1-C5 heterocyclic amido group;
"Linker" is Ci-C6 alkyl, C1-C5 alkoxy, C1-C5 alkylthio, C1-C5 alkoxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido or C6-Ci2 arylamido group;
G is a kind of optionally modified prodrug of commercial drug Lipitor having the following structure VHa-VIId:
Figure imgf000019_0001
Vila Vllb VIIc Vlld
Wherein R10 and R11 are each H, C1-C5 alkoxy, C6-Ci2 aryloxy, C1-C5 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido, C6-Ci2 arylamido, liquid crystal monomer or modified pro-drug;
R12 is cyclopropyl, Ci-C6 alkly, C3-C6 cycloalkyl, Ci-C6 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C6 alkylamino, C6-Ci2 arylamino, Ci-C6 alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-Ci2 heterocyclic aryl or C2-C6 heterocyclic group.
In another preferred embodiment, the present invention provides a method of making a quality-modified polymer having the following structure Villa- Vlllb in the presence of one or two more mixed ruthenium catalysts;
Figure imgf000020_0001
Villa Vlllb (PDCPD)
The present invention provides a process of preparing functional polymers Villa- Vlllb in the presence of one or two more mixed catalysts.
In the third preferred embodiment, the present invention provides a method of making a modified nitrile butadiene rubber (NBR) or styrene-butadiene rubber (SBR) by depolymerization in the presence of one or more mixed catalysts of the present invention at 30-100°C.
In the fourth preferred embodiment, the present invention provides a method of making a depolymerized HNBR (hydrogenated nitrile butadiene rubber) or styrene-butadiene rubber by adding one or more mixed catalysts of the present invention first to carry out depolymerization of NBR, followed by adding hydrogen into the reaction under high pressure for hydrogenation at 60-150°C.
In the fifth preferred embodiment, the present invention provides a method of making a hydrogenated nitrile butadiene rubber (HNBR) or styrene-butadiene rubber by adding hydrogen under high pressure first, followed by adding one or more mixed catalysts of claim 5 at 60-150°C.
In the sixth preferred embodiment, the present invention provides a use of catalysts of the present invention in depolymerization of a rubber comprising at least one carbon-carbon double bond.
In the seventh preferred embodiment, the present invention provides a use of catalysts of the present invention in hydrogenation of a rubber comprising at least one carbon-carbon double bond.
The present invention also provides a useful method of making functional polymers, comprising reacting one or more monomers in the presence of the novel ruthenium catalysts.
In the fifth aspect, the present invention provides a composition of comprising a modified prodrug or functional group G having the following structure IXa-IXc:
Figure imgf000021_0001
IXa IXb
Wherein: r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A, G, "Linker", R11 and R12 each is as defined above.
In the most preferred embodiment of the present invention, wherein a modified prodrug or functional group G having the following structures IXa-IXc:
r =1 or 2; s =1 or 2;
A, "Linker", R10 and R11 each is as defined above;
G is a kind of optionally modified pro-drug of Lipitor having the following structure VHa-VIId:
Figure imgf000021_0002
Vila VI lb VIIc Vlld
Wherein R12 is cyclopropyl, Ci-C6 alkly, C3-C6 cycloalkyl, Ci-C6 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C6 alkylamino, C6-Ci2 arylamino, Ci-C6 alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heterocyclic aryl or C2-C6 heterocyclic group.
The present invention relates to two classes of novel carbene ligands and ruthenium complexes as catalysts in uses of carrying out metathesis reactions effectively, e.g., preparation of the high strength and/or stiffness polymer materials, functional polymers linked with small molecule pro-drugs and liquid crystal materials.
Currently, the present invention provides the following significant achievements: 1. Two classes of novel carbene ligands and ruthenium complexes have been designed and prepared, which has different structure and activity with five or six coordinate bonds, especially for the new Ru complexes with six coordinate bonds to form at least one "Ru-N" coordinate bond from the new developed ligands la or lb. Moreover, the electronic and steric effect of different substituted ligands on the catalytic activity and stability of various new Ru complexes have been studied, and it is found that some of novel Ru catalysts in the present invention have much better catalytic selectivity and variable physical diversity than Grubbs and Hoveyda catalysts in the ROMP and RCM reactions.
2. The experimental results show that some of novel Ru catalysts in the present invention have high activity and selectivity for different olefin ROMP and RCM reactions, so the invention provides a useful synthetic method of carrying out olefin metathesis reactions effectively in preparation of polymer materials and pharmaceutical intermediates.
3. The present invention provides several developed methods for preparation of carbene ligands and Ru catalysts at lower cost, and it also provides some efficient methods for preparation of various functional polymer materials with different chemical and physical properties.
4. The present invention provides several developed processes of conducting ROMP reaction with one or two more mixed of novel active Ru catalysts for preparation of the high-strength polymer materials and some functional polymers linked with small molecule pro-drugs and/or liquid crystal materials.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 : Single-crystal X-ray Structure of Ru Catalyst 8m.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises two novel classes of carbene ligands and ruthenium complexes as catalysts for metathesis reactions. To study the electronic and steric effects of multi- substituted benzylidene ligands on the stability and activity of Ru complexes, based on the following reported procedure in Schemes 1-3, different kinds of the complex ligands (3a-3bf, 5a- 5j, 7a-7r, 9a-9j) have been prepared and reacted with the Ru complex 1 to obtain different kinds of new Ru complex (4a-4bf, 6a-6j, 8a-8r, lOa-lOj, lla-llr). During preparation and activity evaluation of various Ru complexes with various substituted 2-aminobenzylidene ligands in the following Schemes 4-8, different kinds of the electron-withdrawing and/or electron-donating effect and steric effect on the stability and selective activity for ROMP and RCM reactions have been found as shown in Schemes 9-16 and Tables 1-6.
Significant electronic effect of various substituted benzylidene ligands on the stability of Ru complexes: Based on different described synthetic methods and procedures in Schemes 1-3, there are different kinds of new olefin or carbene ligands (Ia-Ib) and Ru complexes (Ila-IIb) prepared in the present invention. Moreover, significant substituent effect of different substituted benzylidene ligands on the stability and activity of Ru complexes has been observed and developed selectively for ROMP and RCM reactions, and some novel Ru catalysts have been prepared much more active and selective than prior reported Ru catalysts for different kinds of ROMP and RCM reactions.
According to previously described synthetic methods, various new Ru complexes 4a-4bf have been prepared by the reaction listed in Scheme 4, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 4:
Figure imgf000024_0001
Some selected structure of prepared ligands 3a-3bf and corresponding ruthenium complexes 4a-4bf (la: Cy = cyclohexyl, lb = 2,4,6-trimethylbenzene) are listed as follows:
Figure imgf000025_0001
Figure imgf000026_0001

Figure imgf000027_0001

Figure imgf000028_0001

Figure imgf000029_0001
Figure imgf000029_0002
Figure imgf000030_0001
According to previously described synthetic methods, various new Ru complexes 6a-6j have been prepared by the reaction listed in Scheme 5, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 5:
Figure imgf000031_0001
Some selected structure of prepared ligands 5a- 5j and corresponding ruthenium complexes 6a-6j (la: Cy = cyclohexyl, lb = 2,4,6,- trimethylbenzene) are listed as follows:
Figure imgf000031_0002
Figure imgf000032_0001
6g 6h 6j (Unstable)
According to previously described synthetic methods, various new Ru complexes 8a-8r have been prepared by the reaction listed in Scheme 6, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 6:
Figure imgf000032_0002
SM 7a-7r 7a-7r
Figure imgf000032_0003
(Mes = 2,4,6-trimethylphenyl) 8a-8r
Some selected structure of prepared ligands 7a-7r and corresponding ruthenium complexes 8a-8r (la: Cy = cyclohexyl, lb = 2,4,6,- trimethylbenzene) are listed as follows:
Figure imgf000033_0001
Figure imgf000034_0001
8g 8j
Figure imgf000034_0002
The structure of Ru catalyst 8m is confirmed by single-crystal X-ray as shown ure 1. According to previously described synthetic methods, various new Ru complexes lOa-lOj have been prepared by the reaction listed in Scheme 7, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 7:
Figure imgf000035_0001
SM 9a-9 9a-9j
Figure imgf000035_0002
(Mes = 2,4,6-trimethylbenzene) lOa-lOj
Some selected structure of prepared ligands 9a-9j and corresponding ruthenium complexes lOa-lOj (la: Cy = cyclohexyl, lb = 2,4,6,- trimethylbenzene) are listed as follows:
Figure imgf000036_0001
According to previously described synthetic methods, various new Ru complexes lla-llr have been prepared by the reaction listed in Scheme 8, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 8:
Figure imgf000037_0001
Ru catalyst (Ila) 11 (Ru catalyst Ila)
(n = 0, p = 0) = 0, p = l)
Figure imgf000037_0002
Ru catalyst (lib) 11 (Ru catalyst lib)
(n = 0, p = 0) (n = 0, p = l)
Some selected structure of prepared ruthenium complexes lla-llr (la: Cy cyclohexyl, lb = 2,4,6,- trimethylbenzene) is listed as follows:
Figure imgf000037_0003
11a 11 b 11c
Figure imgf000037_0004
Figure imgf000038_0001
Figure imgf000038_0002
Two alternative production procedures for preparation of some highly active metathesis catalysts: In order to prepare different kinds of Ru catalyst at lower cost, based on some references (Zhan et al, US20070043180A1 and WO2007003135A1) and new process development as described in Schemes 9 and 10, there is the following alternative procedure developed in Scheme 9 for scale-up production of different Ru catalysts in the present invention.
Figure imgf000039_0001
l lh
Scheme 9: A convenient route for preparation of some Ru complexes In Scheme 9, the starting material 4-SM was reacted with sodium ethoxide to produce carbene intermediate 4-1 first, followed by reacting with RuCl2(PPh3)3 directly to form Ru complex intermediate 4-2. The triphenylphosphine ligand (PPh3) of Ru intermediate 4-2 was replaced by another ligand PCy3 (4-3, Hid) to form a new Ru complex 4i. The phosphine ligand of Ru intermediate 4-2 or 4i was further replaced by an NHC ligand (H2IMes, 4-4, Ilia) to form another Ru complex 4j . The Ru complex 4j could directly react with another ligand 4-chloro pyridine (4-5) to make the Ru complex llh.
Figure imgf000040_0001
4x 4aa
Scheme 10: A convenient route for preparation of some Ru complexes In Scheme 10, The Ru complex 2h is prepared by the reaction of reagents SM-2b and RuCl2(PPh3)3 in anhydrous DCM in a three-neck flask filled with inert gas (Ar), followed by reacting the Ru complex 2h with complex ligand 3x (la) to form another Ru complex 2j (Va) in a flask filled with inert gas (Ar). The triphenylphosphine ligand (PPh3) of Ru intermediate 2j was replaced by another phosphine ligand PCy3 (4-3, Hid) to form a new Ru complex 4x. The phosphine ligand of Ru intermediate 2j or 4x was further replaced by another HC ligand (H2IMes, 4-4, Ilia) to form another Ru complex 4aa.
So far, to study the relative activity and catalytic selectivity of above prepared catalysts 4a-4bj, 6a-6j, 8a-8u, lOa-lOj, and lla-llr, two olefin substrates 15 and 17 in Equations 1 and 2 were chosen for RCM reactions, and different kinds of cyclic olefin substrates 19, 21, 23, 25, 27, 29 and 31 in Equations 3-9 were selected for ROMP reactions, and the kinetic results of different conducted RCM and ROMP reactions for each new catalyst are listed in Tables 1, 2, 3, 4 and 5, respectively. Other eight prior known Ru catalysts la-lb and 2a-2f listed in Scheme 1 are also selected for evaluation of metathesis activity study with various substrates 15, 17, 19, 21, 23, 25, 27, 29 and 31 in comparison to all new Ru catalysts in the present invention.
The evaluation of catalytic activity for RCM in Equation 1 with different catalysts 4a-4bj, 6a-6j, 8a-8u, lOa-lOj, and lla-llr has been done under the same reaction condition, and the valuable experimental data for different Ru catalysts are selected and listed in Tables 1-1 to 1-4, respectively.
Equation
Figure imgf000041_0001
15 16
Table 1-1 : Activity Results of Some Selected Complexes 4a-4bj for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
lO min 30 min 1.5 hr 3.0 hr
1 4a 40 81 98
2 4b 52 85 98
3 4e 0 0 0
4 4f 84 94 96 100
5 4g 94 100
6 4h 3 5 11 16
7 4u 96 100
8 4y 43 66 87 94
9 4aa 21 59 82 92
10 4ab 94 100
11 4ac 70 90 100
12 4af 93 97
13 4aj 95 99
14 4ap 71 82 93 98
15 4at 24 48 73 100
16 4ba 62 73 79 85
17 4bb 100
18 4bc 94 100
19 4bd 68 81 84 89
20 4be 100
Among Ru complexes 4a-4bj, only some of new complexes (such as 4f, 4g, 4u, 4ab, 4aj, 4bb and 4be) show high catalytic activity, the rest of them not listed in Table 1-1 have lower or very poor activities for RCM reaction. Based on the determined results in Table 1-1, the activity of Ru complexes 4a-4bj for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 3a-3bj. However, some of complexes 4a-4bj non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-2. Activity Results of Some Selected Complexes 6a-6j for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 6e 0 0 0 0
2 6h 95 100
3 6j 45 70 89 95
4 2e 0 0 0 0
Among complexes 6a-6j, only a Ru complexes 6h shows high catalytic activity and much better than the known catalyst 2e, the rest of them not listed in Table 1-2 have worse or very poor activities. Based on the determined results in Table 1-2, the activity of Ru complexes 6a-6j for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 5a-5j. However, some of complexes 6a-6j non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-3. Activity Results of Some Selected Complexes 8a-8u for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 8b 73 79 98
2 8c 21 36 53 66
3 8g 0 0 0 0
4 8h 96 98 99
5 8t 53 76 88 99
6 8u 79 93 100
7 2c 47 69 82 92
Among complexes 8a-8u, only a few complexes (such as 8b, 8h and 8r) show good activity and much better than the reported catalyst 2c, the rest of them not listed in Table 1-3 have worse or very poor activities. Based on the determined results in Table 1-3, the activity of Ru complexes 8a-8u for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 7a-7u. However, some of non-active complexes 8a-8u for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-4: Activity Results of Some Selected Complexes lOa-lOj for Substrate 15
Conversion (% by HPLC)
Catalyst
lO min 30 min 1.5 hr 3.0 hr
1 10c 90 99
2 lOd 96 100
3 lOe 91 96 100
4 lOg 84 99
5 10j 86 92 99
6 2d 62 78 90 98
Among complexes lOa-lOj, several complexes (such as 10c, lOd, lOe and lOg) show good or high catalytic activity and much better than the known catalyst 2d, the rest of them not listed in Table 1-4 have worse or very poor activities. Based on the determined results in Table 1-4, the activity of Ru complexes lOa-lOj for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 9a-9j. However, some of non-active complexes 10a- lOj for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-5: Activity Results of Some Selected Complexes lla-llr for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 lib 38 57 60 61
2 lie 44 57 65 68
3 lip 39 43 45 45
4 llq 32 34 38 40
Among complexes lla-llr, only a few complexes (such as 11c, lie and lip) show lower catalytic activity, the rest of them not listed in Table 1-5 have worse or very poor activities. Based on the determined results in Table 1-5, the activity of Ru complexes lla-llr for RCM is significantly affected by the electronic effect of different substituented pyridine ligands. However, some of complexes lla-llr non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
In order to find some new catalysts with better activity and selectivity it is designed to carry out a RCM reaction with a phenyl-substituted diene substrate 17 as shown in Equation 2 instead of unsubstituted diene substrate 15 for further evaluation of some active catalysts selected from the catalysts 4a-4bj, 6a-6j, 8a-8u, lOa-lOj, and lla-llr according to activity results in Tables 1-1 to 1-5. The experimental results of RCM activity for substrate 17 are listed in Tables 2.
Equation 2:
o Ru catalyst
Figure imgf000044_0001
17 18
Table 2: Activity Results of Some Selected Ru Complexes for Substrate 17
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 4f 67 86 94 99
2 4g 61 78 86 98
5 4ab 63 85 96 99
6 4ad 51 68 79 95
7 4af 72 86 92 99
8 4be 49 73 86 91
9 6h 70 88 90 96
10 8h 75 88 96 99
11 10a 42 65 81 98
12 10c 71 82 85 92
13 lOd 82 94 95 100
14 lOf 35 63 83 99
15 lOg 46 69 84 100
To develop more effective ROMP catalysts and prepare better quality of new functional polymers, and also better to measure the difference of various active Ru catalysts, the evaluation of catalytic activity for different ROMP reactions in Equations 3-9 with different catalysts 4a-4bj, 6a-6j, 8a-8u, lOa-lOj, and lla-llr has been done under the same reaction condition, and some valuable results for different Ru catalysts are selected or listed in Tables 3 to 6, respectively. Based on the broad test, it is useful to find some active and selective catalysts for ROMP and RCM reactions, respectively.
Equation 3 :
Figure imgf000045_0001
19 20
After screening with most of new Ru catalysts, it is found that some catalys as 8g and 8m could selectively catalyze the ROMP reaction effectively.
Equation 4:
Ru catalyst
Figure imgf000045_0002
(0.1% molar)
21 22
After screening with most of new Ru catalysts, it is found that some catalysts such as 4d and 8j could catalyze the ROMP reaction effectively.
Equation 5 :
Figure imgf000045_0003
(0.1% molar)
23 24
The ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 8b and 8h of the present invention have better activity and selectivity for norbornene (23) polymerization. Catalytic polymerization was completed in 10-60 min, and the polymer product (24) has better tensile-strength when it is prepared as film.
Equation 6:
Figure imgf000046_0001
The ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 4ag, 4ar, 4au, 8a, 8b, 8c, 8h, 8m and 8q of the present invention have better activity and selectivity for DCPD (25) polymerization. The ROMP polymerization was completed in 5-60 min for different Ru catalysts. The reaction temperature is preferred to be 40-60 °C . By using one or two more mixed catalysts, it is surprised to obtain the high strength and high stiffness polymer PDCPD.
The property tests of various PDCPD (26) samples in the present invention show that several PDCPD products have more better tensile strength (55-62Mpa) and flexural strength (78-83Mpa) than those of commercial PDCPD products such as "Pentam, Metton, and Prometa" (tensile strength: 40-50Mpa, and flexural strength: 66-75Mpa) reported by other companies prepared with their own ROMP catalysts in Japan and USA, which advantage in the present invention will provide an alternative method of making high-quality of PDCPD material for broad uses in polymer industry.
Equation 7:
Figure imgf000046_0002
27 28
Some selected structure of prepared polymers 28a-28g is listed as follows, and ROMP results are listed in Table 3 :
Figure imgf000047_0001
28e 28f 28g
Table 3 : Selected ROMP results
Figure imgf000047_0002
The results of Table 3 show that, small molecule liquid crystal or pro-drug monomer can react with new Ru catalysts selected from the present invention to form polymerized macromolecule liquid crystal (28c and 28d) and polymer-linked prodrugs (28e, 28f and 28g) with special properties and applications. The results of activity test show that several new catalysts (such as 4d, 4f, 6g and 11a) of the present invention have better catalytic activity for olefin monomers (27a-27g), and the ROMP reactions were completed in 5-15 hrs. Yield is better than 80% with optimized polymerization conditions in the presence of new Ru catalyst 4d.
The results of polymerization test show that different Ru catalysts of the present invention have significantly different activity and selectivity for different cyclo-olefin monomers. In particular, some new Ru catalysts (e.g., 4d and 6g) have lower catalytic activities in RCM reaction, but have very good activity in ROMP reactions, which demonstrates that several new Ru catalysts in the present invention have the high selectivity and catalytic activity for ROMP and RCM, respectively.
Equation 8:
Figure imgf000048_0001
29 30
Some selected structure of prepared polymers 30a-30n is listed as follows, and some selected ROMP results are listed in Table 4:
Figure imgf000049_0001
30a 30b 30c 30d
Figure imgf000049_0002
30j 30k 30m 30n
Table 4: Selected ROMP results
Figure imgf000049_0003
The results in Table 4 show that most of cyclo-olefin monomers with different functional groups (29a-29n) were polymerized in the presence of new Ru catalysts such as 4d or 6g selected from the present invention to form functional polymers with different chemical and physical properties.
Equation 9:
Figure imgf000050_0001
Some selected structure of prepared polymers 32a-32m is listed as follows, and some selected ROMP results are listed in Table 5:
Figure imgf000050_0002
32a 32b 32c 32d
Figure imgf000050_0003
32e 32f 32g 32h
Figure imgf000050_0004
32i 32j 32k 32m Table 5 : Selected ROMP results
Figure imgf000051_0001
The results in Table 5 show that hat most of cyclo-olefin monomers with different functional groups (31a-31m) were polymerized in the presence of new Ru catalyst 4d selected from the present invention to form functional polymers with different chemical and physical properties. Moreover, several products 32a, 32b, 32c, and 34m could be used to form film with high strength (over 50 Mpa).
The catalysts of the present invention can be used for depolymerization of a rubber comprising at least one carbon-carbon double bond. The depolymerization is conducted by metathesis reaction of carbon-carbon double bond in the rubber in the presence of one or more of catalysts of the present invention. The depolymerized rubber has lower molecular weight and lower mooney viscosity, which can be better used at lower temperature as lower as -40°C.
The catalysts of the present invention can be used in hydrogenation of a rubber comprising at least one carbon-carbon double bond. The carbon-carbon double bond in the rubber is hydrogenated under high pressure of hydrogen in the presence of one or more of catalysts of the present invention. The hydrogenated rubber is obtained and could be used as more stable and higher strength rubber.
The rubber comprising at least one carbon-carbon double bond can be depolymerized, and followed by hydrogenation under high pressure of hydrogen to produce a lower molecular weight and lower mooney viscosity rubber in the presence of one or more catalysts of the present invention, which can be used at lower temperature as lower as -55°C.
The rubber comprising at least one carbon-carbon double bond can be hydrogenated under high pressure of hydrogen and depolymerized simultaneously in the presence of one or more catalysts of the present invention, which can be used at lower temperature as lower as -55°C.
The representative examples of rubbers include but not limited to nitrile butadiene rubber, polybutadiene rubber, styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS) or any rubber containing carbon-carbon double bond.
For example, the BR is depolymerized by using catalyst 4ab at 30°C-100°C as shown in Equation 10:, and the physical properties of depolymerized NBR are listed in Table 6.
Equation 10:
Figure imgf000052_0001
(In Equation, where q > q')
Table 6: Depolymerization Results by Ru Catalysts
Figure imgf000052_0002
Notes: Mw and Mn: Molecular weight. RM: Raw Material.
So far, it is determined that the molecular weight (Mw) and Mooney viscosity of various nitrile butadiene rubber (e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850) are significantly reduced down about 30-70% as needed by metathesis depolymerization in chlorobenzene or chloroform in the presence of catalysts of the present invention (e.g., catalyst 4ab selected from 4a-4bj, 6a-6j, 8g-8u, lOe-lOg).
Equation 11 :
Figure imgf000053_0001
In Equation 11, q > (t + u).
The process for Equation 11 was carried out by adding Ru metathesis catalyst (4aa) for depolymerization first at 60°C-150°C, followed by adding hydrogen under high pressure 2.0-15MPa for hydrogenation in chlorobenzene. It is determined that the molecular weight (Mw) and Mooney viscosity of various nitrile butadiene rubbers (e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850) are significantly reduced down about 30-70%) as needed by depolymerization in chlorobenzene or chloroform in the presence of the catalysts of the present invention (e.g., 4a-4bj, 8g-8u, lOe-lOg), and the hydrogenation degree is determined to be between 90-99.5%) as needed. The depolymerization and hydrogenation results are listed in the following Table 7.
Table 7: Depolymerization and Hydrogenation Results by Ru Catalysts
Figure imgf000053_0002
Notes: Mw and Mn: Molecular weight; [H]: Hydrogenation;
RM: Raw Material, which is undepolymerized and unhydrogenated. Equation 12:
-H2C-CH=CH-CH2j—(CH2-CH-^-(-CH2-CH ^
CH2 CN
CH3
1) H2
2) Ru Catalyst(s)
Y (Hydrogenation)
H2C-CH2-CH2-CH2-7- H2C-CH=CH-CH2-)-r{cH2-CH -fcH2-CH -
\ f ' ' U I ' Γ % s
CH2 CN
CH3
In Equation 12, q > (t'+u').
The process for Equation 12 was carried out by adding hydrogen under high pressure 2.0-15MPa first, followed by adding Ru metathesis catalyst (4aa) to conduct hydrogenation and depolymerization simultaneously in chlorobenzene at 60°C-150°C . It is determined that the hydrogenation degree is determined to be between 90-99.5% as needed (determined by IHNMR), and the molecular weight (Mw) and Mooney viscosity of various nitrile butadiene rubbers (e.g., commercially available from Zeon company (Japan) in trade name N41, DN3335, DN3350, and DN2850) are reduced down about 10-50% as needed by depolymerization in chlorobenzene or chloroform in the presence of catalysts (e.g., 4a-4bj, 8g-8u, lOe-lOg). The depolymerization and hydrogenation results are listed in Table 8.
Table 8: Selected Hydrogenation and Depolymerization Results by Ru Catalysts
Figure imgf000054_0001
RM: Raw Material, which is undepolymerized and unhydrogenated.
Based on the results from Equation 10 to Equation 12, it is determined that the molecular weight (Mw) and Mooney viscosity of various NBR brands (e.g., N41, DN3335, DN3350, and DN2850) are obviously reduced about 30-70% as needed by metathesis depolymerization and hydrogenation by adding hydrogen in chlorobenzene or chloroform in the presence of the Ru catalysts (e.g., 4a-4bj, 8g-8u, lOe-lOg) to obtain different kinds of HNBR products as needed with lower molecular weight (Mooney viscosity range: 20-100MU) and high hydrogenation degree (90-99.5%).
So far, it is found that most of the new developed Ru catalysts (4a-4bj, 6a-6j, 8a-8u, lOa-lOj) can be used to reduce molecular weight of the nitrile butadiene rubber (NBR) and butyl rubber by catalytical depolymerization. Furthermore, the quality-modified hydrogenated nitrile butadiene rubber (HNBR) with different molecular weight has been prepared by adding different new Ru catalyst and hydrogen (H2) under high pressure (2.0-15Mpa) in some organic solvents such as chlorobenzene or chloroform solution. Just as mentioned above, the depolymerized NBR can be used in lower temperature as lower as -40 °C , and the depolymerized and hydrogenated NBR (HNBR) can be used in a temperature as lower as -55 °C with an improved strength and a better UV-resistance.
Based on our broad study, it is found that some of novel Ru catalysts (such as 4a-4bj, 8g-8u, lOa-lOj) have good activity for metathesis depolymerization to prepare different kinds of lower molecular NBR, followed by hydrogenation under high pressure of hydrogen (preferred between 4-9Mpa) to prepare high hydrogenation degree and various molecular weight of HNBR products.
Overall, based on the activity and selectivity studies in equations 1-10, it is found that some of novel Ru catalysts such as 4d, 4f, 4g, 4ab, 6h, 8g, 8h, 10c and lOe have much better activity and selectivity than other tested and reported metathesis catalysts for the ROMP and RCM reactions, respectively. Moreover, it is found that the electronic effect of multi- substituted benzylidene ligands on the activity and selectivity of Ru complexes is one of the most important factors for the development of new active and selective metathesis catalysts for ROMP and RCM reactions. Based on the intensive study, the present invention provides some useful methods of carrying out ROMP, RCM, CM, and ADMET reactions with one or two more mixed of novel active Ru catalysts for preparation of some functional polymers, lower molecular weight rubbers and/or pharmaceutical intermediates, respectively. EXAMPLES
General: Infrared (IR) spectra were recorded on a Fourier Transform AVATAR™ 360 E.S.P™ spectrophotometer (Unit: cm"1). Bands are characterized as broad (br), strong (s), medium (m), and weak (w). 1H NMR spectra were recorded on a Varian-400 (400 MHz) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the solvent resonance as the internal standard (CDC13: 7.26 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling constants (Hz), integration, and assignment. 19F and 31P NMR spectra were recorded on a Varian-400 (400 MHz) and Gemini-2000 (300MHz) spectrometers. The chemical shifts of the fluoro resonances were determined relative to trifluoroacetic acid as the external standard (CF3CO2H: 0.00 ppm), and the chemical shifts of the phosphorus resonances were determined relative to phosphoric acid as the external standard (H3PO4: 0.00 ppm). Mass spectra were obtained at Thermo Finnigan LCQ Advantage. Unless otherwise noted, all reactions were conducted in oven- (135°C) and flame-dried glassware with vacuum-line techniques under an inert atmosphere of dry Ar. THF and Et20 were distilled from sodium metal dried flask, DCM, pentane, and hexanes were distilled from calcium hydride. Different substituted 2-alkoxystyrene ligands were prepared according to literature procedures as shown in Schemes 1-3. SM-Ia and SM-Ib chemicals were obtained from commercial sources or ordered by custom synthesis from Zannan Pharma Ltd., China. General procedures for preparation of different Ru complexes are described in examples 1 and 2, respectively. General procedures for evaluation of the RCM and ROMP reactions are described in examples 104-107, respectively.
Example 1
Synthesis of Ru complex 4a
SM-3a (5.0mmol) was added into a 50 mL of three-neck round-bottom flask filled with inert gas (Ar), and followed by adding DME (10 mL) and deionized water (3 mL). K2CO3 (1.5 eq) was added and the solution was N2 protected. The reaction was heated to 85 °C , 2,4,6-Trivinyl-cyclotriboroxane pyridine complex (0.5 eq) and Pd(PPh3)4 (2%) were added until completed overnight, (monitored by TLC). The reaction mixture was filtered and extracted by DCM twice, then purified by flash column eluting with a gradient solvent (PE/EA 400/1 to 100/1) and dried under vacuum to obtain 0.9g of yellow oil products 3a (yield: 86%). The product was confirmed by 1HNMR.
Ligand 3a 1H- MR (400 MHz, CDC13): δ 7.56 (d, J = 7.5 Hz, 1H, aromatic H), 7.37-7.18 (m, 5H, aromatic H, CH=CH2), 7.02 (dd, J = 17.4 Hz, 10.8 Hz, 1H, CH=CH2), 6.76-6.64 (m, 3H, aromatic H), 5.72 (d, J = 17.4 Hz, 1H, CH=CH2), 5.34 (d, J= 10.8 Hz, 1H, CH=CH2), 4.33 (s, 2H, NCH2), 3.83 (s, 1H, H).
(H2IMes)(PCy3)Cl2Ru=CHPh (formula lb, 860mg, l .Ommol) and CuCl (270 mg, 2.5mmol, 2.5 eq) were added into a 100 mL of two-neck round-bottom flask filled with inert gas (Ar), and followed by adding DCM (15 mL) and ligand 3a (250 mg, 1.2mmol, 1.2 eq) into the DCM solution at 20-25°C. The reaction was stirred until completed in 30-60 min. (monitored by TLC). The reaction mixture was filtered and concentrated, then purified by flash column eluting with a gradient solvent (Pentane/DCM 2/1 to DCM). The purified solid product was washed with methanol, and dried under vacuum to obtain 27mg of green solid product 4a, yield: 4%. The green product was confirmed by 1HNMR.
Ru complex (4a) 1HNMR (400 MHz, CDC13): δ 19.09 (s, lH, Ru=CH), 7.51-6.70 (m, 13H), 5.31 (m, 1H), 4.30 (d, J = 12.9 Hz, 1H), 4.04 (s, 4H, NCH2CH2N), 3.61 (d, J= 12.9 Hz, 1H), 2.45 (s, 12H), 2.33 (s, 6H). Example 2
Synthesis of Ru complex 4b
The synthetic procedure for preparation of ligand 3b is the same as in Example 1 in 5.0 mmol scale. 1.15g of yellow oil product 3b was obtained (yield: 91%).
Ligand 3b 1H- MR (400 MHz, CDC13): δ 7.54 (d, J = 6.6 Hz, 1H), 7.27-7.23 (m, 3H), 7.02 (dd, J = 11.1 Hz, 17.0 Hz, 1H), 6.87-6.84 (m, 2H), 6.75-6.72 (m, 2H), 5.69 (dd, J = 1.5 Hz, 17.0 Hz, 1H), 5.35 (dd, J = 1.5 Hz, 11.1 Hz, 1H), 4.47 (s, 2H), 3.78 (s, 3H), 2.93 (s, 3H).
(PCy3) 2Cl2Ru=CHPh (formula la, 830mg, l .Ommol) and CuCl (270 mg, 2.5mmol, 2.5 eq) were added into a 100 mL of two-neck round-bottom flask filled with inert gas (Ar), and followed by adding DCM (15 mL) and ligand 3b (250 mg, 1.2mmol, 1.2 eq) into the DCM solution at 20-25°C. The reaction was stirred until completed in 30-60 min. (monitored by TLC). The reaction mixture was filtered and concentrated, then purified by flash column eluting with a gradient solvent (Pentane/DCM 2/1 to DCM). The purified solid product was washed with methanol, and dried under vacuum to obtain 195mg of green solid product 4b, yield: 29%. The green product was confirmed by 1HNMR.
Ru complex (4b) 1HNMR (400 MHz, CDC13): δ 19.31 (d, J = 8.4 Hz, Ru=CH), 7.57-7.50 (m, 4H), 7.31-7.29 (m, 1H), 7.15 (d, J = 5.6 Hz, 1H), 6.84-6.81 (m, 2H), 5.78 (d, J = 12.0 Hz, 1H), 3.71 (s, 3H), 3.62 (d, J = 12.0 Hz, 1H), 2.51 (s, 3H), 2.22-1.13 (m, 33H, PCy3).
Example 3
Synthesis of Ru complex 4c
The synthetic procedure for preparation of ligand 3c is the same as in Example 1 in 5.0 mmol scale. 0.66g of yellow oil product 3c was obtained (yield: 54%).
Ligand 3c 1H- MR (400 MHz, CDC13): δ 7.56 (d, J = 7.5 Hz, 1H, aromatic H), 7.34-7.26 (m, 3H, aromatic H, CH=CH2), 7.13 (d, J = 9 Hz, 1H, CH=CH2), 6.98 (dd, J = 17.4 Hz, 10.8 Hz, 1H, CH=CH2), 6.56 (d, J = 9 Hz, 1H, CH=CH2), 5.71 (dd, J = 17.4 Hz, 1.2 Hz, 1H, CH=CH2), 5.35 (dd, J= 10.8 Hz, 1.2 Hz, 1H, CH=CH2), 4.30 (s, 2H, NCH2), 3.86 (s, 1H, H).
The procedure for preparation of Ru complex 4c is the same as in Example 1 in 1.0 mmol scale. 35 mg of green solid product 4c was obtained (yield: 5%).
Ru complex (4c) 1HNMR (400 MHz): δ 19.09 (s, lH, Ru=CH), 7.50-6.69 (m, 12H), 5.27 (m, 1H), 4.33 (d, J = 12.9 Hz, 1H), 4.04 (s, 4H, NCH2CH2N), 3.59 (d, J = 12.9 Hz, 1H), 2.45 (s, 12H), 2.37 (s, 6H).
Example 4
Synthesis of Ru complex 4d
The synthetic procedure for preparation of ligand 3d is the same as in Example 1 in 5.0 mmol scale. 0.74g of yellow oil product 3d was obtained (yield: 62%).
Ligand 3d 1H- MR (400 MHz, CDC13): δ 7.32-7.23 (m, 2H), 7.04-6.91 (m, 2H), 6.82 (dd, J = 2.0 Hz, 6.6 Hz, 2H), 6.62 (dd, J = 2.4 Hz, 6.6 Hz, 2H), 5.73 (d, J = 17.1 Hz, 1H), 5.39 (d, J= 11.1 Hz, 1H), 4.25 (s, 2H), 3.77 (s, 3H).
The procedure for preparation of Ru complex 4d is the same as in Example 1 in
1.0 mmol scale. 231 mg of green solid product 4d was obtained (yield: 32%).
Ru complex (4d) 1HNMR (400 MHz, CDC13): δ 18.68 (s, Ru=CH), 7.23-6.65 (m, 10H), 6.36 (dd, J = 2.8, 9.6 Hz, 1H), 6.03 (d, J = 12.8 Hz, 1H), 4.14-3.90 (m, 4H, NCH2CH2N), 3.85 (s, 3H), 3.47 (d, J= 12.8 Hz, 1H), 2.89-1.62 (m, 18H).
Example 5
Synthesis of Ru complex 4e
The structure of ligand 3e is the same as 3d for preparation of Ru complex 4e, just another Ru complex reagent la was used instead of Ru reagent lb.
The procedure for preparation of Ru complex 4e is the same as in Example 2 in
1.0 mmol scale. 243 mg of green solid product 4e was obtained (35% yield).
Ru complex (4e) 1HNMR (400 MHz, CDC13): δ 19.28 (d, J = 8.4 Hz, Ru=CH), 7.45 (d, J = 8.8 Hz, 2H), 7.31-7.16 (m, 3H), 6.83 (d, J = 8.8 Hz, 2H), 5.13 (t, J = 12.4 Hz, 1H), 7.96 (d, J = 12.4 Hz, 1H), 3.85 (d, J = 12.4 Hz, 1H), 3.80 (s, 3H), 2.28-1.24 (m, 33H, PCy3).
Example 6
Synthesis of Ru complex 4f
The synthetic procedure for preparation of ligand 3f is the same as in Example 1 in 5.0 mmol scale. 0.79g of yellow oil product 3f was obtained (yield: 63%). Ligand 3f 1H- MR (400 MHz, CDC13): δ 7.21 (m, 2H), 6.94 (m, 2H), 6.85 (m, 2H), 6.73 (m, 2H), 5.68 (dd, J = 1.2 Hz, 16.8 Hz, 1H), 5.38 (dd, J = 1.5 Hz, 11.4 Hz, 1H), 4.40 (s, 2H), 3.77 (s, 3H), 2.89 (s, 3H).
The procedure for preparation of Ru complex 4f is the same as in Example 1 in 1.0 mmol scale. 103 mg of green solid product 4f was obtained (yield: 14%).
Ru complex (4f) 1HNMR (400 MHz, CDC13): δ 18.99 (s, Ru=CH), 7.48-7.44 (m, 1H), 7.19-6.86 (m, 7H), 6.72-6.66 (m, 1H), 5.29 (t, J = 13.2 Hz, 1H), 4.19-3.58 (m, 8H), 2.52-2.37 (m, 18H). Example 7
Synthesis of Ru complex 4g
The synthetic procedure for preparation of ligand 3g is the same as in Example 1 in 5.0 mmol scale. 0.70g of yellow oil product 3g was obtained (yield: 56%). The product 3g is confirmed by LC-MS (M+H+): m/z calculated: 285.1, found: 285.1, and directly used for preparation of Ru complex 4g.
The procedure for preparation of Ru complex 4g is the same as in Example 1 in 1.0 mmol scale. 61 mg of green solid product 4g was obtained (yield: 8%).
Ru complex (4g) 1HNMR (400 MHz, CDC13): δ 19.11 (s, lH, Ru=CH), 8.36 (dd, J = 2.0, 8.0 Hz, 1H), 7.29-6.65 (m, 10H ), 5.30 (t, J = 13.6 Hz, 1H), 4.23 (d, J = 13.2 Hz, 1H), 4.10 (s, 3H), 3.80 (s, 4H, NCH2CH2N), 3.69 (d, J = 13.2 Hz, 1H), 2.65-2.08 (m, 18H).
Example 8
Synthesis of Ru complex 4h
The synthetic procedure for preparation of ligand 3h is the same as in Example 1 in 5.0 mmol scale. 0.47g of yellow solid product 3h was obtained (yield: 32%).
Ligand 3h 1H- MR (400 MHz, CDC13): δ 7.32 (dd, J= 5.6 Hz, 8.0 Hz, 1H), 7.25 (dd, J = 2.8 Hz, 10.4 Hz, 1H), 7.00-6.92 (m, 2H), 6.34 (s, 2H), 5.72 (d, J = 17.2 Hz, 1H), 5.38 (d, J= 11.2 Hz, 1H), 4.23 (s, 2H), 3.68 (s, 3H), 2.24 (s, 6H). The procedure for preparation of Ru complex 4h is the same as in Example 1 in 1.0 mmol scale. 315 mg of green solid product 4h was obtained (yield: 42%).
Ru complex (4h) 1HNMR (400 MHz, CDC13): 19.02 (s, 1H, Ru=CH), 7.21-6.82 (m, 8H), 6.40 (dd, J = 9.6 Hz, 1.6 Hz), 5.21 (m, 1H), 4.06-4.00 (m, 5H), 3.70 (s, 3H), 3.54 (d, J= 13.2 Hz, 1H), 2.48-2.18 (m, 24H).
Example 9
Synthesis of Ru complex 4j
The synthetic procedure for preparation of ligand 3j is the same as in Example 1 in 5.0 mmol scale. 0.91g of yellow liquid product 3j was obtained (yield: 93%).
Ligand 3j 1H- MR (400 MHz, CDC13): δ 7.34-7.26 (m, 2H), 7.22-7.13 (m 2H), 6.98-6.95 (m, 2H), 6.81 (m, 1H), 6.70-6.68 (m, 1H), 5.73 (d, J= 17.2 Hz, 1H), 5.36 (d, J= 11.2 Hz, 1H), 4.32 (s, 2H), 2.81 (m, 1H), 1.24 (d, J= 6.8 Hz, 6H).
The procedure for preparation of Ru complex 4j is the same as in Example 1 in 1.0 mmol scale. 353 mg of green solid product 4j was obtained (yield: 48%).
Ru complex (4j) 1H- MR (400 MHz, CDC13): δ 18.88 (s, lH, Ru=CH), 7.57-6.44 (m, 11H), 5.36 (t, J = 13.2 Hz, 1H), 4.16-4.02 (m, 5H), 4.01 (d, J = 13.2 Hz, 1H), 2.75-2.00 (m, 19H), 1.01-0.90 (m, 6H). Example 10
Synthesis of Ru complex 4k
The synthetic procedure for preparation of ligand 3k is the same as in Example 1 in 5.0 mmol scale. 0.57g of yellow oil product 3k was obtained (yield: 83%).
Ligand 3k 1H- MR (400 MHz, CDC13): δ = 7.26 Hz) : 7.317 (dd, 1H, J = 6 Hz,8.4 Hz), 7.256 (dd, J = 2.8 Hz, 10.4 Hz, 1H), 7.094-7.017 (m, 3H), 6.961 (td, J = 2.8 Hz, 8.8 Hz, 1H), 6.873 (t, 1H, J = 6.8 Hz), 5.735 (d, J = 17.2 Hz 1H,), 5.412 (d, J = 10.8 Hz, 1H), 4.133(s, 2H), 2.276(s, 6H).
The procedure for preparation of Ru complex 4k is the same as in Example 1 in 1.0 mmol scale. 490 mg of green solid product 4k was obtained (yield: 68%). Ru complex (4k) 1HNMR (400 MHz, CDC13): δ 18.90 (s, 1H, Ru=CH), 7.27-6.77 (m, 9H), 6.41 (d, J = 8.0 Hz, 1H), 5.43 (t, J = 13.2 Hz, 1H), 4.18-4.00 (m, 5H), 3.25 (d, J = 13.6 Hz, 1H), 2.76-1.27 (m, 24H).
Example 11
Synthesis of Ru complex 4m
The synthetic procedure for preparation of ligand 3m is the same as in Example 1 in 5.0 mmol scale. 0.76g of yellow oil product 3m was obtained (yield: 49%). The product 3m is confirmed by LC-MS (M+H+): m/z calculated: 311.2, found: 311.2, and directly used for preparation of the Ru complex 4m.
The procedure for preparation of Ru complex 4m is the same as in Example 1 in 1.0 mmol scale. 404 mg of green solid product 4m was obtained (yield: 52%).
Ru complex (4m) 1HNMR (400 MHz, CDC13): δ 18.95 (s, lH, Ru=CH), 7.43-6.36 (m, 10H), 4.00 (m, 6H), 2.67-2.06 (m, 20H), 0.90-0.83 (m, 12H).
Example 12
Synthesis of Ru complex 4n
The synthetic procedure for preparation of ligand 3n is the same as in Example 1 in 5.0 mmol scale. 0.63g of yellow oil product 3n was obtained (yield: 45%).
Ligand 3n 1H- MR (400 MHz, CDC13): δ 7.33 (dd, J= 6.8 Hz, 6.8 Hz, 1H), 7.26 (d, J = 11.6 Hz, 1H), 7.08 (dd, J = 10.8 Hz, 17.6 Hz, 1H), 6.69 (t, J = 8.4 Hz, 1H), 6.86 (s, 2H), 5.74 (d, J= 17.6 Hz, 1H), 5.42 (d, J= 10.8 Hz, 1H), 4.08 (s, 2H), 2.25 (s, 9H).
The procedure for preparation of Ru complex 4n is the same as in Example 1 in 1.0 mmol scale. 470 mg of green solid product 4n was obtained (yield: 64%).
Ru complex (4n): 1H- MR (400 MHz, CDC13): δ 18.88 (s, lH, Ru=CH), 7.25-6.36 (m, 9H), 5.40 (t, J= 13.2 Hz, 1H), 4.14-4.00 (m, 6H), 2.77-1.90 (m, 27H).
Example 13
Synthesis of Ru complex 4p The synthetic procedure for preparation of ligand 3p is the same as in Example 1 in 5.0 mmol scale. 0.85g of yellow oil product 3p was obtained (yield: 67%).
Ligand 3p 1H- MR (400 MHz, CDC13): δ=7.26Ηζ):7.368 (dd, 1H, J=6.00 Hz, 8.40 Hz), 7.258-7.126 (m, 4H), 7.019-6.922 (m, 3H), 5.632 (dd, 1H, J = 1.20 Hz, 17.60 Hz), 5.287 (dd, 1H, J = 1.20 Hz, 11.20 Hz), 4.072 (s, 2H), 2. 537 (s, 3H), 2.290 (s, 3H)
The procedure for preparation of Ru complex 4p is the same as in Example 1 in 1.0 mmol scale. 184 mg of green solid product 4p was obtained (yield: 26%).
Ru complex (4p) 1HNMR (400 MHz, CDC13): δ 18.91 (s, lH, Ru=CH), 7.63-6.42 (m, 10H), 5.27 (t, J = 13.2 Hz, 1H), 4.13-4.01 (m, 5H), 3.44 (d, J = 13.2 Hz, 1H), 2.46-2.00 (m, 21H).
Example 14
Synthesis of Ru complex 4q
The synthetic procedure for preparation of ligand 3q is the same as in Example 1 in 5.0 mmol scale. 0.69g of yellow oil product 3q was obtained (yield: 46%).
Ligand 3q 1H- MR (400 MHz, CDC13): δ 7.21 (dd, J = 2.8 Hz, 10.0 Hz, 1H), 7.15 (dd, J = 5.6 Hz, 7.6 Hz, 1H), 6.97-6.88 (m, 2H), 6.39 (s, 2H), 5.68 (d, J = 17.2 Hz, 1H), 5.36 (dd, J = 0.8 Hz, 11.2 Hz, 1H), 4.40 (s, 2H), 3.67 (s, 3H), 2.87 (s, 3H), 2.24 (s, 6H).
The procedure for preparation of Ru complex 4q is the same as in Example 1 in 1.0 mmol scale. 291 mg of green solid product 4q was obtained (yield: 38%).
Ru complex (4q) 1HNMR (400 MHz, CDC13): δ 18.75 (s, lH, Ru=CH), 7.26-6.21 (m, 9H), 4.05-3.85 (m, 5H), 3.72 (s, 3H), 3.34 (d, J = 13.2 Hz, 1H), 2.82-0.95 (m, 30H).
Example 15
Synthesis of Ru complex 4r
The synthetic procedure for preparation of ligand 3r is the same as in Example 1 in 5.0 mmol scale. 0.55g of yellow oil product 3r was obtained (yield: 44%).
Ligand 3r 1H- MR (400 MHz, CDC13): δ 7.33-7.25 (m, 2H), 7.00-6.93 (m, 2H), 6.84 (bd, J= 8.4 Hz, 2H), 6.55 (dd, J= 4.4 Hz, 9.6 Hz, 1H), 5.74 (d, J= 17.2 Hz, 1H), 5.40 (d, J= 11.2 Hz, 1H), 4.29 (s,2H), 3.46 (bs, 1H), 2.12 (s, 3H).
The procedure for preparation of Ru complex 4r is the same as in Example 1 in 1.0 mmol scale. 101 mg of green solid product 4r was obtained (yield: 14%).
Ru complex (4r) 1HNMR (400 MHz, CDC13): δ 18.89 (s, lH, Ru=CH), 7.69-6.43 (m, 10H), 5.23 (dd, J = 13.2, 11.3 Hz, 1H), 4.16-3.94 (m, 5H), 3.46 (d, J = 11.3 Hz, 1H), 2.62-1.00 (m, 21H).
Example 16
Synthesis of Ru complex 4s
The synthetic procedure for preparation of ligand 3s is the same as in Example 1 in 5.0 mmol scale. 0.83g of yellow oil product 3s was obtained (yield: 51%).
Ligand 3s 1H- MR (400 MHz, CDC13): δ 7.30 (dd, J = 6.0 Hz, 8.5 Hz, 1H), 7.23 (dd, J= 3.0 Hz, 10.0 Hz, 1H), 6.70-6.90 (m, 2H), 6.79 (d, J= 8.5 Hz, 2H), 6.58 (d, J = 8.5 Hz, 2H), 5.70 (d, J= 18.0 Hz, 1H), 5.37 (d, J= 11.0 Hz, 1H), 4.23 (s, 2H), 3.88 (t, J = 6.5 Hz, 2H) , 1.73 (m, 2H), 1.44 (m, 2H), 1.35-1.31 (m, 4H), 0.90 (t, J = 6.0 Hz, 3H).
The procedure for preparation of Ru complex 4s is the same as in Example 1 in 1.0 mmol scale. 679 mg of green solid product 4s was obtained (yield: 85%).
Ru complex (4s) 1HNMR (400 MHz, CDC13): δ 18.68 (s, lH, Ru=CH), 7.28-6.42 (m, 10H), 6.37 (d, J= 8.5 Hz, 1H), 5.05 (m, 1H), 4.06-3.93 (m, 7H,), 3.57 (d, J= 12.8 Hz, 1H), 2.89-1.29 (m, 29H).
Example 17
Synthesis of Ru complex 4t
The synthetic procedure for preparation of ligand 3t is the same as in Example 1 in 5.0 mmol scale. 0.67g of yellow product 3t was obtained (yield: 38%). The product 3t is confirmed by LC-MS (M+H ): m/z calculated: 339.2, found: 339.2, and directly used for preparation of the Ru complex 4t.
The procedure for preparation of Ru complex 4t is the same as in Example 1 in 1.0 mmol scale. 185 mg of green solid product 4t was obtained (yield: 23%).
Ru complex (4t) 1HNMR (300 MHz, CDC13): δ 18.97 (s, lH, Ru=CH), 8.54-8.45
(m, 2H), 6.66-6.96 (m, 8H), 4.16-4.10 (m, 1H), 4.03 (s, 4H, NCH2CH2N), 2.63-1.75 (m, 22H), 0.92 (d, J= 7.6Hz), 0.83 (d, J= 7.6Hz).
Example 18
Synthesis of Ru complex 4u
The synthetic procedure for preparation of ligand 3u is the same as in Example 1 in 5.0 mmol scale. 0.39g of yellow oil product 3u was obtained (yield: 28%).
Ligand 3u 1H- MR (400 MHz, CDC13): δ 7.53 (d, J = 2.0 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 7.28-7.26 (m, 1H), 7.21-7.12 (m, 3H), 7.03 (dd, J = 10.8 Hz, 17.6Hz, 1H), 5.73 (d, J= 17.6 Hz, 1H), 5.43 (d, J= 10.8 Hz, 1H), 4.07 (s, 2H), 3.26 (m, 2H), 1.25 (d, J= 6.4 Hz, 12 H).
The procedure for preparation of Ru complex 4u is the same as in Example 1 in 1.0 mmol scale. 254 mg of green solid product 4u was obtained (yield: 32%).
Ru complex (4u) 1HNMR (300 MHz, CDC13): δ 19.03 (s, lH, Ru=CH), 7.48-6.63 (m, 10H), 5.53 (m, 1H), 4.81-4.78 (m, 1H), 4.00 (s, 4H, NCH2CH2N), 2.51-2.49 (m, 1H), 2.51-2.32 (m, 18H), 1.12 (d, J= 7.6Hz), 1.04 (d, J= 7.6Hz).
Example 19
Synthesis of Ru complex 4v
The synthetic procedure for preparation of ligand 3v is the same as in Example 1 in 5.0 mmol scale. 1.08g of yellow oil product 3v was obtained (yield: 81%).
Ligand 3v 1H- MR (400 MHz, CDC13): δ 7.56 (d, J = 7.2 Hz, 1H), 7.34 (dd, J =
1.6 Hz, 7.6 Hz, 1H), 7.30-7.26 (m, 2H), 7.03 (dd, J = 11.2 Hz, 17.2 Hz, 1H),
6.86-6.80 (m, 2H), 6.68-6.62 (m, 2H), 5.72 (dd, J = 1.2 Hz, 17.2 Hz, 1H), 5.33 (dd, J = 1.2 Hz, 11.2 Hz, 1H), 4.56 (m, 1H), 4.36 (s, 2H), 1.33 (d, J= 6 Hz, 6H). The procedure for preparation of Ru complex 4v is the same as in Example 1 in 1.0 mmol scale. 73 mg of green solid product 4v was obtained (yield: 10%).
Ru complex (4v) 1HNMR (400 MHz, CDC13): δ 18.97 (s, Ru=CH), 7.50-6.58 (m, 11H), 5.26-3.52 (m, 8H), 3.48-2.07 (m, 18H), 1.23 (d, J= 6.4 Hz, 6H).
Example 20
Synthesis of Ru complex 4w
The structure of ligand 3w is the same as 3v for preparation of Ru complex 4w, just another Ru complex reagent la was used instead of Ru reagent lb.
The procedure for preparation of Ru complex 4w is the same as in Example 2 in 1.0 mmol scale. 219 mg of green solid product 4w was obtained (yield: 31%).
Ru complex (4w) 1HNMR (400 MHz, CDC13): δ 19.56 (d, J = 9.9 Hz, Ru=CH), 8.20 (d, J= 8.1 Hz, 1H), 7.66-6.84 (m, 6H), 5.46 (d, J= 12 Hz, 1H), 5.22 (t, J= 6 Hz, 1H), 4.56 (m, 1H), 3.95 (d, J= 12.0 Hz, 1H), 2.34-0.87 (m, 39H, PCy3).
Example 21
Synthesis of Ru complex 4x
The synthetic procedure for preparation of ligand 3x is the same as in Example 1 in 5.0 mmol scale. 0.96g of yellow oil product 3x was obtained (yield: 76%).
Ligand 3x 1H- MR (400 MHz, CDC13): δ 7.27 (dd, J = 4.5 Hz, 6.15 Hz, 1H), 7.21-7.17 (m, 1H), 6.95-6.88 (m, 2H), 6.82-6.75 (m, 2H), 6.64-6.60 (m, 1H), 6.55 (d, J = 5.7 Hz, 1H), 5.66 (d, J = 12.9 Hz, 1H), 5.32 (d, J = 8.1 Hz, 1H), 4.48 (m, 1H), 4.26 (s, 2H), 1.27 (d, J= 4.5 Hz, 6H).
The procedure for preparation of Ru complex 4x is the same as in Example 2 in 1.0 mmol scale. 420 mg of green solid product 4x was obtained (yield: 58%).
Ru complex (4x) 1HNMR (400 MHz, CDC13): δ 19.55 (d, J = 9.9 Hz, Ru=CH), 8.14 (d, J = 8.1 Hz, 1H), 7.36-6.83 (m, 6H), 5.46 (d, J = 12.0 Hz, 1H), 5.13 (t, J = 6.0 Hz, 1H), 4.56 (m, 1H), 3.90 (d, J= 12.0 Hz, 1H), 2.30-1.25 (m, 39H, PCy3).
Example 22 Synthesis of Ru complex 4y
The synthetic procedure for preparation of ligand 3y is the same as in Example 1 in 5.0 mmol scale. 0.58g of yellow oil product 3y was obtained (yield: 47%).
Ligand 3y 1H- MR (400 MHz, CDC13): δ 7.33 (dd, J =5.6 Hz, 8.4Hz, 1H), 7.25 (dd, J = 2.8 Hz, 10 Hz, 1H), 7.05-6.82 (m, 3H), 6.81 (dd, J = 1.6 Hz, 8 Hz, 1H), 6.74-6.69 (m, 1H), 6.62 (dd, J = 1.6 Hz, 8Hz, 1H), 5.57 (d, J = 17.6 Hz, 1H), 5.40 (d, J= 11.2 Hz, 1H), 4.31 (s, 2H), 3.84 (s, 3H).
The procedure for preparation of Ru complex 4y is the same as in Example 1 in 1.0 mmol scale. 267 mg of green solid product 4y was obtained (yield: 37%).
Ru complex (4y): 1HNMR (400 MHz, CDC13): δ 18.83 (s, Ru=CH), 7.50-6.39 (m, 11H), 5.21 (t, J= 12.4 Hz, 1H), 4.69-3.46 (m, 9H), 2.62-2.08 (m, 18H).
Example 23
Synthesis of Ru complex 4z
The structure of ligand 3z is the same as 3y for preparation of Ru complex 4z, just another Ru complex intermediate la was used instead of Ru intermediate lb.
The procedure for preparation of Ru complex 4z is the same as in Example 2 in 1.0 mmol scale. 362 mg of green solid product 4z was obtained (yield: 52%).
Ru complex (4z) 1HNMR (400 MHz, CDC13): δ 19.35 (d, J = 9.9 Hz, Ru=CH), 8.11 (d, J = 8.1 Hz, 1H), 7.34-6.85 (m, 6H), 5.48 (d, J = 12.0 Hz, 1H), 5.27 (t, J = 6 Hz, 1H), 3.93 (d, J= 12.0 Hz, 1H), 3.88 (s, 3H), 2.33-1.24 (m, 33H, PCy3).
Example 24
Synthesis of Ru complex 4aa
The structure of ligand 3aa is the same as 3x for preparation of Ru complex 4aa, just another Ru complex intermediate lb was used instead of Ru intermediate la.
The procedure for preparation of Ru complex 4aa is the same as in Example 1 in 1.0 mmol scale. 631 mg of green solid product 4aa was obtained (yield: 84%).
Ru complex (4aa) 1HNMR (400 MHz, CDC13): δ 18.89 (s, Ru=CH), 7.60-6.45 (m, 11H), 5.13-3.52 (m, 8H), 2.95-2.10 (m, 18H), 0.95 (d, J= 6.4 Hz, 6H)
Example 25
Synthesis of Ru complex 4ab
The synthetic procedure for preparation of ligand 3ab is the same as in Example
1 in 5.0 mmol scale. 0.32g of yellow oil product 3ab was obtained (yield: 26%).
Ligand 3ab 1H- MR (400 MHz, CDC13): δ 8.36 (d, J= 2.8 Hz, 1H), 8.05 (dd, J = 2.8 Hz, 8.4 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.01 (dd, J = 10.5 Hz, 17.1 Hz, 1H), 6.85-6.69 (m, 3H), 6.44 (d, J = 7.5 Hz, 1H), 5.86 (dd, J = 0.9 Hz, 17.1 Hz, 1H,), 5.53 (dd, J= 0.9Hz, 10.5 Hz, 1H), 4.46 (s, 2H), 3.87 (s, 3H)
The procedure for preparation of Ru complex 4ab is the same as in Example 1 in 1.0 mmol scale. 300 mg of green solid product 4ab was obtained (yield: 40%).
Ru complex (4ab) 1HNMR (400 MHz, CDC13): δ 16.52 (s, Ru=CH), 7.58 (m, 1H), 7.09 (s, 4H), 6.93-6.60 (m, 6H ), 4.52 (m, 1H), 4.35 (s, 2H), 4.18 (s, 4H, NCH2CH2N), 3.89 (s, 6H), 2.49 (s, 12H), 2.40 (s, 6H).
Example 26
Synthesis of Ru complex 4ac
The synthetic procedure for preparation of ligand 3ac is the same as in Example 1 in 5.0 mmol scale. 1.09g of yellow oil product 3ac was obtained (yield: 91%).
Ligand 3ac 1H- MR (400 MHz, CDC13): δ 7.49 (s, 1H, H), 7.27 (d, J= 7.5 Hz, 1H, aromatic H), 7.09-7.00 (m, 2H, aromatic H, CH=CH2), 6.88-6.63 (m, 5H, aromatic H), 5.75 (d, J= 17.4 Hz, 1H, CH=CH2), 5.38 (d, J= 10.8 Hz, 1H, CH=CH2), 4.28 (s, 2H, NCH2), 3.81 (s, 6H, OCH3).
The procedure for preparation of Ru complex 4ac is the same as in Example 1 in
1.0 mmol scale. 367 mg of green solid product 4ac was obtained (yield: 50%).
Ru complex (4ac) 1HNMR (400 MHz, CDC13): δ 19.03 (s, Ru=CH), 8.38 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 16.0 Hz, 1H), 7.44 (d, J = 7.6 Hz, 1H), 7.21-7.03 (m, 5H), 6.83-6.59 (m, 3H), 5.24 (t, J =12.0 Hz, 1H), 4.66 (d, J =12.0 Hz, 1H), 4.45 (m, 1H), 4.20-4.05 (m, 4H, NCH2CH2N), 3.62 (d, J =12.0 Hz, 1H), 2.69-2.03 (m, 18H), 1.18 (d, J= 5.6 Hz, 6H).
Example 27
Synthesis of Ru complex 4ad
The synthetic procedure for preparation of ligand 3ad is the same as in Example
1 in 5.0 mmol scale. l .Olg of yellow oil product 3ad was obtained (yield: 79%).
Ligand 3ad 1H- MR (400 MHz, CDC13): δ 7.48 (d, J = 2.1 Hz, 1H, aromatic H), 7.27-7.24 (m, 1H, aromatic H), 7.04 (dd, J= 18Hz, 10.8 Hz, 1H, CH=CH2), 6.85-6.79 (m, 3H, aromatic H), 6.67-6.61 (m, 2H, aromatic H), 5.74 (dd, J = 18 Hz, 1.2 Hz, 1H, CH=CH2), 5.28 (dd, J = 10.8 Hz, 1.2 Hz, 1H, CH=CH2), 4.59-4.53 (m, 2H, OCH, H), 4.29 (s, 2H, NCH2), 3.86 (s, 3H, OCH3), 1.37 (d, J= 6.4 Hz, 6H, OCH(CH3)2).
The procedure for preparation of Ru complex 4ad is the same as in Example 1 in 1.0 mmol scale. 374 mg of green solid product 4ad was obtained (yield: 49%).
Ru complex (4ad) 1HNMR (400 MHz, CDC13): δ 16.52 (s, Ru=CH), 7.59 (m, 1H), 7.09 (s, 4H), 6.92-6.84 (m, 4H ), 6.75-6.66 (m, 2H), 4.59 (m, 1H), 4.35 (s, 2H), 4.18 (s, 4H, NCH2CH2N), 3.89 (s, 3H), 2.49 (s, 12H), 2.40 (s, 6H, 18H), 0.93 (m, 6H).
Example 28
Synthesis of Ru complex 4ae
The synthetic procedure for preparation of ligand 3ae is the same as in Example 1 in 5.0 mmol scale. 0.32g of yellow oil product 3ae was obtained (yield: 27%).
Ligand 3ae 1HNMR (400 MHz, CDC13): δ 8.36 (d, J = 2.4 Hz, 1H), 8.05 (dd, J = 2.4 Hz, 8.4 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.01 (dd, J = 10.8 Hz, 17.1 Hz, 1H), 6.84-6.75 (m, 2H), 6.71-6.65 (m, 2H), 6.42 (dd, J= 1.8 Hz, 7.8 Hz, 1H), 5.85 (dd, J = 0.9 Hz, 17.1 Hz, 1H), 5.53 (dd, J = 0.9 Hz, 10.8 Hz, 1H), 4.58 (m, 1H), 4.47 (s, 1H), 1.36 (d, J= 6.0 Hz, 6H).
The procedure for preparation of Ru complex 4ae is the same as in Example 1 in 1.0 mmol scale. 389 mg of green solid product 4ae was obtained (yield: 50%). Ru complex (4ae) 1HNMR (400 MHz, CDC13): δ 19.03 (s,lH, Ru=CH), 8.38 (d, J= 2.0 Hz, 1H), 7.69 (d, J= 16.0 Hz, 1H), 7.44 (d, J= 7.6 Hz, 1H), 7.21-7.03 (m, 5H), 6.83-6.59 (m, 3H), 5.24 (t, J =12.0 Hz, 1H), 4.66 (d, J =12.0 Hz, 1H), 4.45 (m, 1H), 4.20-4.05 (m, 4H, NCH2CH2N), 3.62 (d, J =12.0 Hz, 1H), 2.69-2.03 (m, 18H), 1.18 (d, J= 5.6 Hz, 6H).
Example 29
Synthesis of Ru complex 4af
The synthetic procedure for preparation of ligand 3af is the same as in Example 1 in 5.0 mmol scale. 0.76g of yellow oil product 3af was obtained (yield: 65%).
Ligand 3af 1H- MR (400 MHz, CDC13): δ 7.38-7.34 (m, 2H, aromatic H), 7.22-7.10 (m, 2H, aromatic H, CH=CH2), 7.01-6.88 (m, 4H, aromatic H), 5.63 (d, J = 17.1 Hz, 1H, CH=CH2), 5.29 (d, J= 10.8 Hz, 1H, CH=CH2), 4.20 (s, 2H, NCH2), 3.88 (s, 3H, OCH3), 2.63 (s, 3H, NCH3).
The procedure for preparation of Ru complex 4af is the same as in Example 1 in 1.0 mmol scale. I l l mg of green solid product 4af was obtained (yield: 15%).
Ru complex (4af) 1HNMR (400 MHz, CDC13): δ 18.54 (s, lH, Ru=CH), 7.45 (d, J= 8.0 Hz, 1H), 7.24-7.19 (m, 4H), 7.06-6.96 (m, 6H), 6.14 (d, J= 13.2 Hz, 1H), 5.39 (d, J= 13.2 Hz, 1H), 4.07-3.77 (m, 7H), 3.52 (s, 3H), 2.65-2.30 (m, 18H).
Example 30
Synthesis of Ru complex 4ag
The synthetic procedure for preparation of ligand 3ag is the same as in Example 1 in 5.0 mmol scale. 0.84g of yellow oil product 3ag was obtained (yield: 76%).
Ligand 3ag 1H- MR (400 MHz, CDC13): δ = 7.26 Hz): 7.32 (dd, J = 5.70 Hz, 8.40 Hz, 1H), 7.24 (dd, J = 9.9 Hz, 2.4 Hz, 1H), 7.03-6.90 (m, 2H), 6.54-6.39 (m, 3H), 5.71 (dd, J = 1.2 Hz, 17.4 Hz, 1H), 5.37 (dd, J = 1.2 Hz, 10.8 Hz, 1H), 4.25 (s, 2H), 4.07 (bs, 1H), 3.81 (s, 3H), 3.76 (s, 3H).
The procedure for preparation of Ru complex 4ag is the same as in Example 1 in 1.0 mmol scale. 302 mg of green solid product 4ag was obtained (40% yield).
Ru complex (4ag) 1HNMR (400 MHz, CDC13): δ 18.83 (s, lH, Ru=CH), 7.36-6.14 (m, 10H), 5.12 (t, J = 12.4 Hz, 1H), 4.50-3.42 (m, 12H), 2.62-2.05 (m, 18H).
Example 31
Synthesis of Ru complex 4ah
The synthetic procedure for preparation of ligand 3ah is the same as in Example 1 in 5.0 mmol scale. 0.46g of yellow oil product 3ah was obtained (yield: 38%).
Ligand 3ah 1H- MR (400 MHz, CDC13): δ 7.34-7.23 (m, 2H), 7.03-6.91 (m, 2H), 6.69(dd, J = 1.2 Hz, 8.10 Hz , 1H), 7.52-6.45 (m, 2H), 5.72 (d, J = 17.4 Hz, 1H), 5.38 (d, J= 11.4 Hz, 1H), 4.32 (bs, 1H), 4.28 (s, 2H), 2.27 (s, 3H).
The procedure for preparation of Ru complex 4ah is the same as in Example 1 in 1.0 mmol scale. 376 mg of green solid product 4ah was obtained (yield: 51%).
Ru complex (4ah) 1HNMR (400 MHz, CDC13): δ 18.90 (s, lH, Ru=CH), 7.60-6.36 (m, 10H), 5.25 (t, J = 12.0 Hz, 1H), 4.78 (d, J = 12.0 Hz, 1H), 4.05 (s, 4H, NCH2CH2N), 3.53 (s, 3H), 3.43 (d, J= 12.0 Hz, 1H), 2.56-2.13 (m, 21H).
Example 32
Synthesis of Ru complex 4aj
The synthetic procedure for preparation of ligand 3aj is the same as in Example 1 in 5.0 mmol scale. 1.22g of yellow oil product 3aj was obtained (yield: 90%).
Ligand 3aj 1H- MR (400 MHz, CDC13): δ 7.35-7.21 (m, 2H), 7.03-6.77 (m, 4H), 6.71-6.58 (m, 2H), 5.71 (d, J = 17.7 Hz, 1H), 5.38 (d, J = 11.1 Hz, 1H), 4.31 (s, 2H), 4.06 (q, J= 11.1 Hz, 2H), 1.40 (t, J = 11.1Hz, 3H).
The procedure for preparation of Ru complex 4aj is the same as in Example 2 in 1.0 mmol scale. 390 mg of green solid product 4aj was obtained (yield: 55%).
Ru complex (4aj) 1HNMR (400 MHz, CDC13): δ19.45 (d, J = 9.6 Hz, Ru=CH), 8.18 (d, J = 7.6 Hz, 1H), 7.40-7.33 (m, 2H), 7.21-7.11 (m, 2H), 6.95-6.88 (m, 2H), 5.52 (m, 1H), 5.23 (m, 1H), 4.16-3.94 (m, 3H), 2.36-0.81 (m, 36H, PCy3).
Example 33
Synthesis of Ru complex 4ak
The synthetic procedure for preparation of ligand 3ak is the same as in Example
1 in 5.0 mmol scale. 0.65g of yellow oil product 3ak was obtained (yield: 52%).
Ligand 3ak 1H- MR (400 MHz, CDC13): δ 7.47 (dd, J = 6.0 Hz, 8.4 Hz, 1H), 7.21 (dd, J= 10.4 Hz, 2.4 Hz, 1H), 7.13 (dd, J= 11.2 Hz, 17.2 Hz, 1H), 6.97-6.92 (m, 3H), 6.79 (d, J = 8.4 Hz, 1H), 5.63 (d, J = 17.2 Hz, 1H), 5.28 (d, J = 11.2 Ηζ, ΙΗ), 4.57 (m, 1H), 4.21 (s, 2H), 2.66 (s, 3H), 1.29-1.27 (m, 15H).
The procedure for preparation of Ru complex 4ak is the same as in Example 1 in 1.0 mmol scale. 299 mg of green solid product 4ak was obtained (yield: 37%).
Ru complex (4ak) 1HNMR (400 MHz, CDC13): δ 19.08 (s, lH, Ru=CH), 7.97-6.33 (m, 10H), 5.08 (m, 2H), 4.34 (m, 1H), 4.02 (s, 4H, NCH2CH2N), 3.41 (m, 1H), 2.53-2.31 (m, 18H), 1.29 (s, 9H), 0.89-0.87 (m, 6H).
Example 34
Synthesis of Ru complex 4am
The synthetic procedure for preparation of ligand 3am is the same as in Example 1 in 5.0 mmol scale. 1.10g of yellow oil product 3am was obtained (yield: 86%).
Ligand 3am 1H- MR (400 MHz, CDC13): δ 7.32 (m, 1H), 7.26-7.21 (m, 1H), 7.00-6.93 (m, 2H), 6.52-6.42 (m, 3H), 5.71 (d, J = 17.4 Hz, 1H), 5.37 (d, J = 11.1 Hz, 1H), 4.50 (m, 1H), 4.38 (m, 1H), 4.26 (s, 2H), 1.31 (m, 12H).
The procedure for preparation of Ru complex 4am is the same as in Example 1 in 1.0 mmol scale. 437 mg of green solid product 4am was obtained (yield: 54%).
Ru complex (4am) 1HNMR (400 MHz, CDC13): δ 18.85 (s, lH, Ru=CH), 7.26-6.07 (m, 10H), 5.04 (t, J = 13.2 Hz, 1H), 4.48 (m, 1H), 4.39-4.33 (m, 2H), 4.15-4.02 (m, 4H, NCH2CH2N), 3.65 (m, 1H), 2.66-2.05 (m, 18H), 1.55 (m, 6H) , 1.38 (m, 6H). Example 35
Synthesis of Ru complex 4an
The synthetic procedure for preparation of ligand 3an is the same as in Example 1 in 5.0 mmol scale. 0.66g of yellow oil product 3an was obtained (yield: 41%).
Ligand 3an 1H- MR (400 MHz, CDC13): δ 7.34-7.22 (m, 2H), 7.02-6.93 (m, 2H), 6.70 (d, J= 7.8 Hz, 1H), 6.48-6.43 (m, 1H), 5.71 (d, J= 17.4 Hz, 1H), 5.37 (d, J = 10.8 Hz, 1H), 4.46 (m, 1H), 4.40 (bs, 1H), 4.28 (s, 2H), 2.25 (s, 3H), 1.30 (d, J= 6.0 Hz, 6H).
The procedure for preparation of Ru complex 4an is the same as in Example 1 in 1.0 mmol scale. 359 mg of green solid product 4an was obtained (yield: 46%).
Ru complex (4an) 1HNMR (400 MHz, CDC13): δ 18.98 (s, lH, Ru=CH), 7.66-6.39 (m, 10H), 5.17 (t, J= 13.2 Hz, 1H), 4.71 (d, J= 13.2 Hz, 1H), 4.36 (m, 1H), 4.06 (brs, 4H, NCH2CH2N), 3.42 (d, J = 13.2 Hz, 1H), 2.63-2.09 (m, 21H), 1.09 (m, 6H).
Example 36
Synthesis of Ru complex 4ap
The synthetic procedure for preparation of ligand 3ap is the same as in Example 1 in 5.0 mmol scale. 0.70g of yellow oil product 3ap was obtained (yield: 57%).
Ligand 3ap 1H- MR (400 MHz, CDC13): δ 7.33-7.25 (m, 2H), 7.04 (dd, J = 10.8 Hz, 17.2 Hz, 1H), 6.96-6.92 (m, 1H), 6.79 (d, J = 2.4 Hz, 1H), 6.54 (d, J = 2.4 Hz, 1H), 5.72 (d, J = 17.2 Hz, 1H), 5.37(d, J = 10.8 Hz, 1H), 4.55 (m, 1H), 4.23 (s, 2H), 3.99 (bs, 1H), 1.40 (s, 9H), 1.29 (s, 9H), 1.20 (d, J= 6.0 Hz, 6H). The procedure for preparation of Ru complex 4ap is the same as in Example 1 in
1.0 mmol scale. 380 mg of green solid product 4ap was obtained (yield: 44%).
Ru complex (4ap) 1HNMR (400 MHz, CDC13): δ 18.99 (s, lH, Ru=CH), 7.45-6.36 (m, 9H), 5.05 (m, 2H), 3.98-3.91 (m, 5H), 3.72 (d, J = 13.2 Hz, 1H), 2.48-2.34 (m, 19H), 1.45-0.95 (m, 21H). Example 37
Synthesis of Ru complex 4aq
The synthetic procedure for preparation of ligand 3aq is the same as in Example 1 in 5.0 mmol scale. 0.63g of yellow oil product 3aq was obtained (yield: 52%).
Ligand 3aq 1H- MR (400 MHz, CDC13): δ 7.54 (d, J = 2.0 Hz, 1H), 7.32 (d, J = 8.4 Hz, 1H), 7.23 (dd, J = 2.0 Hz, 8.4 Hz, 1H), 6.98 (dd, J = 11.2 Hz, 17.2 Hz, 1H), 6.89 (td, J = 1.6 Hz, 7.6 Hz, 1H), 6.83 (td, J = 1.6 Hz, 8.0 Hz, 1H), 6.73 (td, J = 1.6 Hz, 8.0Hz, 1H), 6.59 (dd, 7=1.6 Hz, 7.6 Hz, 1H), 5.74 (dd, 7= 0.80 Hz, 17.2 Hz, 1H), 5.40 (dd, 7= 0.80 Hz, 11.2 Hz, 1H), 4.33 (s, 2H), 3.86 (s, 3H).
The procedure for preparation of Ru complex 4aq is the same as in Example 1 in 1.0 mmol scale. 665 mg of green solid product 4aq was obtained (yield: 90%).
Ru complex (4aq) 1H- MR (400 MHz, CDC13): δ 18.75 (s, lH, Ru=CH), 7.50-7.44 (m, 2H), 7.04-6.36 (m, 9H), 5.32-5.21 (m, 1H), 4.65 (d, 7 = 13.2 Hz, 1H), 4.16-4.04 (m, 4H, NCH2CH2N), 3.59 (s, 3H), 3.48 (d, 7= 13.2 Hz, 1H), 2.62-2.32 (m, 18H).
Example 38
Synthesis of Ru complex 4ar
The synthetic procedure for preparation of ligand 3ar is the same as in Example
1 in 5.0 mmol scale. 0.56g of yellow oil product 3ar was obtained (yield: 44%).
Ligand 3ar 1H- MR (400 MHz, CDC13): δ 7.52 (d, 7 = 2.0 Hz, 1H), 7.31 (d, 7 = 8.4 Hz, 1H), 7.22 (dd, 7 = 2.0 Hz, 8.4 Hz, 1H), 6.96 (dd, 7 = 11.2 Hz, 17.2 Hz, 1H), 6.86-6.81 (m, 2H), 6.68 (td, 7= 1.2 Hz, 7.6Hz 1H,), 6.56 (dd, 7= 1.6 Hz, 7.6 Hz, 1H), 5.73 (dd, 7 = 0.8 Hz, 17.2 Hz, 1H,), 5.39 (dd, 7 = 0.8 Hz, 11.2 Hz, 1H), 4.56 (m, 1H), 4.33 (s, 3H), 1.35 (d, 7= 6.0 Hz, 6H).
The procedure for preparation of Ru complex 4ar is the same as in Example 1 in 1.0 mmol scale. 499 mg of green solid product 4ar was obtained (yield: 65%).
Ru complex (4ar) 1HNMR (300 MHz, CDC13): δ 18.82 (s, lH, Ru=CH), 7.47-7.43 (m, 2H), 7.01-6.56 (m, 9H), 5.12-5.09 (m, 1H), 4.56-4.45 (m, 2H), 4.40-4.15 (m, 4H, NCH2CH2N), 3.48-3.45 (m, 1H), 2.64-2.04 (m, 18H), 1.10 (d, J = 6.4 Hz, 6H). Example 39
Synthesis of Ru complex 4as
The synthetic procedure for preparation of ligand 3as is the same as in Example 1 in 5.0 mmol scale. 0.45g of yellow oil product 3as was obtained (yield: 34%).
Ligand 3as 1H- MR (400 MHz, CDC13): δ 8.20 (d, J= 1.5 Hz, 1H), 7.90 (dd, J = 1.5 Hz, 8.0 Hz, 1H), 7.45 (d, J = 8.0 Hz 1H,), 7.01 (dd, J = 11.5 Hz, 17.0 Hz, 1H), 6.83-6.80 (m, 2H), 6.67 (td, J= 2.0 Hz, 7.0 Hz, 1H), 6.52 (dd, J= 2.0 Hz, 7.5 Hz, 1H), 5.80 (d, J = 17.0 Hz, 1H), 5.42 (d, J = 11.5 Hz, 1H), 4.56 (m, 1H), 4.42 (s, 2H), 3.93 (s, 3H), 1.34 (d, J= 6.5 Hz, 6H).
The procedure for preparation of Ru complex 4as is the same as in Example 1 in 1.0 mmol scale. 467 mg of green solid product 4as was obtained (yield: 59%).
Ru complex (4as) 1HNMR (400 MHz, CDC13): δ 18.82 (s, lH, Ru=CH), 8.15 (dd, J = 6.4, 1.2 Hz, 2H), 7.51 (d, J = 1.2 Hz, 1H), 7.44 (d, J = 1.2 Hz, 1H), 7.05-6.99 (m, 5H), 8.15 (d, J = 6.4Hz, 2H), 6.59-6.56 (m, 1H), 5.22 (m, 1H), 4.63 (m, 1H), 4.41(m, lH), 3.96 (m, 4H, NCH2CH2N), 3.55-3.52 (m, 1H), 2.66-2.33 (m, 18H), 1.14 (d, J= 6.4 Hz, 6H).
Example 40
Synthesis of Ru complex 4at
The synthetic procedure for preparation of ligand 3at is the same as in Example 1 in 5.0 mmol scale. 0.53g of yellow oil product 3at was obtained (yield: 33%).
Ligand 3at 1H- MR (400 MHz, CDC13): δ 7.91 (s, 1H), 7.63 (d, J = 8.0 Hz, 1H), 7.56 (d, J= 8.0 Hz, 1H), 7.03 (dd, J= 11.2 Hz, 17.2 Hz, 1H), 6.88-6.82 (m, 2H), 6.74 (t, J = 8.0 Hz, 1H), 6.53 (d, J = 7.6 Hz, 1H), 5.81 (d, J = 17.2 Hz, 1H), 5.49 (d, J = 11.2 Hz, 1H), 4.44 (s, 2H), 3.88(s, 3H), 2.74 (s, 6H). The procedure for preparation of Ru complex 4at is the same as in Example 1 in 1.0 mmol scale. 341 mg of green solid product 4at was obtained (yield: 42%).
Ru complex (4at) 1HNMR (400 MHz, CDC13): δ 19.02 (s, lH, Ru=CH), 7.87 (dd, J = 8.0, 1.2 Hz, 1H), 7.44 (dd, J = 7.2, 1.2 Hz, 1H), 7.25-7.03 (m, 9H), 5.37-5.30 (m, 1H), 4.76-4.74 (m, 1H), 4.16-4.01 (m, 4H, NCH2CH2N), 3.58-3.54 (m, 4H), 2.75 (s, 6H), 2.73-1.98 (m, 18H).
Example 41
Synthesis of Ru complex 4au
The synthetic procedure for preparation of ligand 3au is the same as in Example
1 in 5.0 mmol scale. 0.58g of yellow oil product 3au was obtained (yield: 39%).
Ligand 3au 1H- MR (400 MHz, CDC13): δ 7.93 (s, 1H), 7.64 (d, J= 8.0 Hz, 1H),
7.50 (d, J = 8.0 Hz, 1H), 7.01 (dd, J= 10.8 Hz, 16.8 Hz, 1H), 6.84-6.69 (m, 3H), 6.49
(d, J= 7.6 Hz, 1H), 5.74 (d, J= 16.8 Hz, 1H), 5.47 (d, J= 10.8 Hz, 1H), 4.59-4.53 (m, 1H), 4.43 (s, 2H), 3.14 (t, J = 8 Hz, 4H), 1.51 (m, 4H), 1.36 (d, J = 5.6 Hz, 6H),
1.33-1.27 (m, 4H), 0.90 (t, J= 7.2 Hz, 6H).
The procedure for preparation of Ru complex 4au is the same as in Example 1 in 1.0 mmol scale. 471 mg of green solid product 4au was obtained (yield: 51%).
Ru complex (4au) 1HNMR (300 MHz, CDC13): δ 19.06 (s, lH, Ru=CH), 7.87 (d, J = 7.6Hz, 1H), 7.42 (d, J = 7.6Hz, 1H), 7.29 (d, J = 12.0 Hz, 1H), 7.11-6.56 (m, 8H), 5.22-5.19 (m, 1H), 4.63-4.64 (m, 1H), 4.45-4.42 (m, 1H), 4.14-4.01 (m, 4H, NCH2CH2N), 3.56-3.53 (m, 1H), 3.12-3.07 (m, 4H), 2.67-2.36 (m, 18H), 1.99-1.00 (m, 24H). Example 42
Synthesis of Ru complex 4av
The synthetic procedure for preparation of ligand 3av is the same as in Example 1 in 5.0 mmol scale. 0.65g of white solid product 3av was obtained (yield: 39%).
Ligand 3av 1H- MR (400 MHz, CDC13): δ = 7.26 Hz) : 7.894 (s, 1H), 7.624 (d, lH, J = 8 Hz), 7.553 (d, J = 8 Hz, 1H), 7.017 (dd, J = 10.8 Hz, 17.2 Hz, 1H), 6.844-6.789 (m, 2H), 6.711 (d, J = 8 Hz, 1H), 6.698 (t, J = 8 Hz, 1H), 5.800 (d, J = 17.2 Hz, 1H), 5.493 (d, J = 10.8 Hz, 1H), 4.584 (m, 1H), 4.453 (s, 2H), 2.737 (s, 6H), 1.365 (d, J= 6 Hz, 6H).
The procedure for preparation of Ru complex 4av is the same as in Example 1 in
1.0 mmol scale. 622 mg of green solid product 4av was obtained (yield: 74%).
Ru complex (4av) 1HNMR (300 MHz, CDC13): δ 19.06 (s, lH, Ru=CH), 7.87 (d, J = 7.6Hz, 1H), 7.42 (d, J = 7.6Hz, 1H), 7.11-6.56 (m, 9H), 5.27-5.20 (m, 1H), 4.64-4.61 (m, 1H), 4.46-4.44 (m, 1H), 4.14-4.01 (m, 4H, NCH2CH2N), 3.59-3.56 (m, 1H), 3.12-3.07 (m, 4H), 2.75 (s, 6H), 2.67-2.36 (m, 18H), 1.13 (d, J= 6.0Hz, 6H).
Example 43
Synthesis of Ru complex 4aw
The structure of ligand 3aw is the same as 3av for preparation of Ru complex 4aw, just another Ru complex reagent la was used instead of Ru reagent lb.
The procedure for preparation of Ru complex 4aw is the same as in Example 2 in 1.0 mmol scale. 626 mg of green solid product 4aw was obtained (yield: 77%).
Ru complex (4aw) 1HNMR (400 MHz, CDC13): δ 19.56 (d, J = 9.6 Hz, Ru=CH), 8.21 (d, J = 8.0 Hz, 1H), 8.09 (d, J = 2.0 Hz, 1H), 8.10 (dd, J = 7.6, 2 Hz, 1H), 7.34-6.87 (m, 4H), 5.47-5.44 (m, 1H), 5.33-5.27 (m, 1H), 4.62-4.56 (m, 1H), 3.99-3.96 (m, 1H), 2.80 (s, 6H), 2.30-1.24 (m, 39H, PCy3).
Example 44
Synthesis of Ru complex 4ax
The synthetic procedure for preparation of ligand 3ax is the same as in Example 1 in 5.0 mmol scale. 0.77g of yellow product 3ax was obtained (yield: 55%). The product 3t is confirmed by LC-MS (M+H+): m/z calculated: 431.2, found: 431.2, and directly used for preparation of the Ru complex 4ax.
The procedure for preparation of Ru complex 4ax is the same as in Example 1 in 1.0 mmol scale. 421 mg of green solid product 4ax was obtained (yield: 47%). Ru complex (4ax) 1HNMR (400 MHz, CDC13): δ 18.99 (s, lH, Ru=CH), 7.88 (dd, J = 8.0, 2.0 Hz, 1H), 7.44 (dd, J = 7.2, 1.2 Hz, 1H), 7.28-6.63 (m, 9H), 5.35-5.28 (m, 1H), 4.75-4.72 (m, 1H), 4.16-4.12 (m, 4H, NCH2CH2N), 3.61 (s, 3H), 3.56-3.52 (m, 4H), 3.10-3.06 (m, 4H), 2.63-2.05 (m, 18H), 1.37-0.98 (m, 14H).
Example 45
Synthesis of Ru complex 4ay
The synthetic procedure for preparation of ligand 3ay is the same as in Example 1 in 5.0 mmol scale. 0.56g of yellow oil product 3ay was obtained (yield: 31%).
Ligand 3ay 1H- MR (400 MHz, CDC13): δ 8.02 (d, J= 1.6 Hz, 1H), 7.72 (dd, J =
1.6 Hz, 8.4 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 7.01 (dd, J = 10.8 Hz, 17.6 Hz, 1H), 6.84-6.80 (m, 2H), 6.70 (td, J= 1.2 Hz, 7.6 Hz, 1H), 6.48 (dd, J= 1.2 Hz, 8.0 Hz, 1H), 5.80 (d, J = 17.6 Hz, 1H), 5.48 (d, J= 10.8 Hz, 1H), 4.67 (bs, 1H), 4.58 (m, 1H), 4.44 (s, 2H), 3.22-3.15 (bm, 1H), 1.81-1.77 (bm, 2H), 1.68-1.63 (bm, 2H), 1.36 (d, J = 6 Hz, 6H), 1.32-1.12 (m, 6H).
The procedure for preparation of Ru complex 4ay is the same as in Example 1 in 1.0 mmol scale. 241 mg of green solid product 4ay was obtained (yield: 27%).
Ru complex (4ay) 1HNMR (400 MHz, CDC13): δ 19.03 (s, 1H, Ru=CH), 7.60 (d, J = 7.6 Hz, 1H), 7.43 (d, J = 3.6 Hz, 1H), 7.14 (s, 1H), 7.09-7.00 (m, 5H), 6.81-6.57(m, 3H), 5.22 (m, 1H), 4.64-4.61 (m, 1H), 4.64-4.42 (m, 2H), 4.15-4.02 (m, 4H, NCH2CH2N), 3.16 (m, 1H), 3.17 (m, 1H), 2.67-2.00 (m, 18H), 1.85-1.00 (m, 16H).
Example 46
Synthesis of Ru complex 4ba
The synthetic procedure for preparation of ligand 3ba is the same as in Example 1 in 5.0 mmol scale. 0.96g of yellow oil product 3ba was obtained (yield: 67%).
Ligand 3ba 1H MR (CDC13, 400 MHz): δ 7.23 (m, 4H), 6.92 (m, 2H), 6.80 (m, 1H), 6.67 (m, 2H), 5.68 (d, 1H), 5.39 (d, 1H), 4.64 (s, 2H), 4.06 (s, 2H), 3.75 (s, 3H). The procedure for preparation of Ru complex 4ba is the same as in Example 1 in 1.0 mmol scale. 176 mg of green solid product 4ba was obtained (yield: 22%).
Ru complex (4ba) 1HNMR (400 MHz, CDC13): δ 18.74 (s, IH, Ru=CH), 7.25-7.24 (m, IH), 7.19(s, IH), 7.14-7.04 (m, 7H), 6.93 (s, IH), 6.71 (s, IH), 6.41-6.40 (d, J=9.0 Hz, IH), 6.10-6.07 (d, J=12.0 Hz, IH), 4.52-4.49 (d, J=13.5Hz, IH), 4.33-4.29 (d, J=18.5 Hz, IH), 4.09 (s, 2H), 3.92 (s, 2H), 3.31 (s, 3H), 2.96-2.92 (d, J=19.0Hz, IH), 2.83 (s, 3H), 2.71(s, 3H), 2.47 (s, 3H), 2.39 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H). Example 47
Synthesis of Ru complex 4bb
The synthetic procedure for preparation of ligand 3bb is the same as in Example 1 in 5.0 mmol scale. 1.13g of yellow oil product 3bb was obtained (yield: 71%).
Ligand 3bb 1H MR (CDC13, 400 MHz): δ 7.21 (m, 4H), 6.90 (m, 2H), 6.78 (m, IH), 6.67 (d, 2H), 5.68 (d, IH), 5.38 (d, IH), 5.06 (m, IH), 4.64 (s, 2H), 3.99 (s, 2H), 1.23 (d, 6H).
The procedure for preparation of Ru complex 4bb is the same as in Example 1 in 1.0 mmol scale. 237 mg of green solid product 4bb was obtained (yield: 30%).
Ru complex (4bb) 1HNMR (400 MHz, CDC13): δ 18.74 (s, IH, Ru=CH), 7.27-7.25 (dd, J=8.0, 3.0 Hz, IH), 7.19 (s, IH), 7.14-7.05 (m, 7H), 6.93 (s, IH), 6.71 (s, IH), 6.42-6.40 (d, J=9.0 Hz, IH), 6.07-6.05 (d, J=12.5 Hz, IH), 4.65-4.61 (m, IH), 4.51-4.49 (d, J=12.5 Hz, IH), 4.24-4.20 (d, J=18.0 Hz, IH), 4.10 (s, 2H), 3.92 (s, 2H), 2.90-2.86 (d, J=18 Hz, IH), 2.83 (s, 3H), 2.71 (s, 3H), 2.47 (s, 3H), 2.39 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H), 0.90-0.82 (d, J=33.0, 6.5 Hz, 6H).
Example 48
Synthesis of Ru complex 4bc
The synthetic procedure for preparation of ligand 3bc is the same as in Example 1 in 5.0 mmol scale. 0.74g of yellow oil product 3bc was obtained (yield: 43%). Ligand 3bc 1H MR (CDCI3, 400 MHz): δ 7.23 (m, 2H), 6.92 (m, 2H), 6.81 (m, 2H), 6.67 (m, 2H), 5.67 (d, 1H), 5.37 (d, 1H), 5.05 (m, 1H), 4.57 (s, 2H), 3.98 (s, 2H), 3.77 (s, 3H), 1.22 (d, 6H).
The procedure for preparation of Ru complex 4bc is the same as in Example 1 in 1.0 mmol scale. 578 mg of green solid product 4bc was obtained (yield: 73%).
Ru complex (4bc) 1HNMR (400 MHz, CDC13): δ 18.72 (s, 1H, Ru=CH), 7.24-7.22 (dd, J=8.5, 2.5 Hz, 1H), 7.16 (s, 1H), 7.07-7.04 (m, 4H), 6.91 (s, 1H), 6.75 (s, 1H), 6.66 (s, 1H), 6.64(s, 1H), 6.39-6.38 (d, J=8.0 Hz, 1H), 6.02-6.00 (d, J=12.0 Hz, 1H), 4.64-4.59 (m, 1H), 4.50-4.47 (d, J=13.0 Hz, 1H), 4.13-4.09 (d, J=18 Hz, 1H), 4.08 (s, 2H), 3.90 (s, 2H), 3.83(s, 3H), 2.81 (s, 3H), 2.81-2.79 (d, J=11.5 Hz, 1H), 2.69 (s, 3H), 2.45 (s, 3H), 2.39 (s, 3H), 2.08 (s, 3H), 2.01 (s, 3H), 0.89-0.81 (dd, J=34.0, 6.0 Hz, 6H).
Example 49
Synthesis of Ru complex 4bd
The synthetic procedure for preparation of ligand 3bd is the same as in Example 1 in 5.0 mmol scale. 0.96g of yellow oil product 3bd was obtained (yield: 52%).
Ligand 3bd 1H MR (CDC13, 400 MHz): δ 7.21 (m, 2H), 7.16 (m, 2H ), 6.86 (m, 2H), 6.58 (m, 2H), 5.68 (d, 1H), 5.39 (d, 1H), 5.06 (m, 1H), 4.60 (s, 2H), 3.97 (s, 2H), 1.23 (d, 6H).
The procedure for preparation of Ru complex 4bd is the same as in Example 1 in 1.0 mmol scale. 236 mg of green solid product 4bd was obtained (yield: 29%).
Ru complex (4bd) 1HNMR (400 MHz, CDC13): δ 18.72 (s, 1H, Ru=CH), 7.28-7.26 (m, 1H), 7.19 (s, 1H), 7.10-7.05 (m, 6H), 6.94 (s, 1H), 6.82 (s, 1H), 6.41-6.39 (d, J=9.5 Hz, 1H), 6.07-6.04 (d, J=12.0 Hz, 1H), 4.68-4.64 (m, 1H), 4.45.4.43 (d, J=12.5 Hz, 1H), 4.24-4.20 (d, J=18.0 Hz, 1H), 4.09 (s, 2H), 3.93(s, 2H), 2.91-2.87 (d, J=18.5 Hz, 1H), 2.81 (s, 3H), 2.70 (s, 3H), 2.47 (s, 6H), 2.10 (s, 3H), 2.03 (s, 3H), 0.93-0.87 (dd, J=24.0, 7.0 Hz, 6H). Example 50
Synthesis of Ru complex 4be
The synthetic procedure for preparation of ligand 3be is the same as in Example 1 in 5.0 mmol scale. 1.46g of yellow oil product 3be was obtained (yield: 84%).
Ligand 3be H MR (CDC13, 400 MHz): δ 7.23 (m, 2H), 6.91 (m, 4H), 6.61 (m, 2H), 5.68 (d, 1H), 5.38 (d, 1H), 5.05 (m, 1H), 4.58 (s, 2H), 3.95 (s, 2H), 1.23 (d, 6H).
The procedure for preparation of Ru complex 4be is the same as in Example 1 in 1.0 mmol scale. 396 mg of green solid product 4be was obtained (yield: 49%).
Ru complex (4be) 1HNMR (400 MHz, CDC13): δ 18.71 (s, 1H, Ru=CH), 7.29-7.25 (dd, J=8.5, 2.5 Hz, 1H), 7.19 (s, 1H), 7.13-7.06 (m, 4H), 6.94 (s, 1H), 6.82-6.77 (m, 3H), 6.42-6.39 (dd, J=9.5, 2.5 Hz, 1H), 6.08-6.05 (d, J=13.0 Hz, 1H), 4.66-4.64 (m, 1H), 4.47-4.45 (d, J=12.5 Hz, 1H), 4.21-4.18 (d, J=18 Hz, 1H), 4.10 (s, 2H), 3.93 (s, 2H), 3.89-3.86 (d, J=18 Hz, 1H), 2.83 (s, 3H), 2.70 (s, 3H), 2.48 (s, 3H), 2.42 (s, 3H), 2.11 (s, 3H), 2.02 (s, 3H), 0.92-0.85 (dd, J=26.5, 7.0 Hz, 3H).
Example 51
Synthesis of Ru complex 4bf
The synthetic procedure for preparation of ligand 3bf is the same as in Example 1 in 5.0 mmol scale. 0.68g of yellow oil product 3bf was obtained (yield: 51%).
Ligand 3bf 1H NMR (CDC13, 400 MHz): δ 7.26 (m, 1H), 7.22 (m, 2H), 6.92 (m, 1H), 5.68 (d, 1H), 5.37 (d, 1H), 5.09 (m, 1H), 3.74 (s, 2H), 3.26 (s, 2H), 2.30 (m, 3H), 1.26 (d, 6H).
The procedure for preparation of Ru complex 4bf is the same as in Example 1 in 1.0 mmol scale. 76 mg of green solid product 4bf was obtained (yield: 10%).
Ru complex (4bf) 1HNMR (400 MHz, CDC13): δ 18.54 (s, 1H, Ru=CH), 7.16-6.87 (m, 7H), 6.15-6.13 (dd, J=10.0, 2.0 Hz, 1H), 5.44-5.41 (d, J=13.5 Hz, 1H), 4.76-4.71 (m, 1H), 4.37-4.34 (d, J=15.5 Hz, 1H), 3.96 (s, 4H, NCH2CH2N), 3.07-3.05 (d, J=13 Hz, 1H), 2.75-2.40 (m, 18H), 1.66 (s, 3H), 1.21-1.17 (dd, J=13.0, 6.5 Hz, 6H). Example 52
Synthesis of Ru complex 4bg
The synthetic procedure for preparation of ligand 3bg is the same as in Example 1 in 5.0 mmol scale. 0.83g of yellow oil product 3bg was obtained (yield: 59%).
Ligand 3bg 1H MR (CDC13, 400 MHz): δ 7. 24 (m, 2H), 6.93 (m, 2H), 6.70 (m, 1H), 6.30 (m, 2H), 5.71 (d, 1H), 5.40 (d, 1H), 4.58 (s, 1H), 4.44 (m, 1H), 4.29 (s, 2H), 1.28 (d, 6H).
The procedure for preparation of Ru complex 4bg is the same as in Example 1 in 1.0 mmol scale. 302mg of green solid product 4bg was obtained (yield: 39%).
Ru complex (4bg) 1HNMR (400 MHz, CDC13): δ 18.91 (s, 1H, Ru=CH), 7.60-7.58 (dd, J = 9.5, 2.5 Hz, 1H), 7.24-7.20 (m, 1H), 7.13-7.05 (m, 3H), 6.94-6.92 (dd, J= 8.0, 6.0 Hz, 1H), 6.80 (brs, 1H), 6.74-6.70 (m, 1H), 6.64-6.61 (dd, J= 9.0, 5.0 Hz, 1H), 6.45-6.43 (dd, J = 10.5, 3.0 Hz, 1H), 5.20-5.15 (t, J = 13.5, 1H, NCH2), 4.69-4.67 (d, J = 12.5 Hz, 1H, NCH2), 4.38-4.33 (m, 1H, OCH(CH3)2), 4.12-4.08(m, 4H, NCH2CH2N), 3.47-3.45 (d, J = 12.5 Hz, 1H, H), 2.65 (s, 6H), 2.56 (s, 6H), 2.26 (s, 3H), 2.09 (s, 3H), 1.14-1.12 (dd, J= 6.0, 4.0 Hz, 6H, OCH(CH3)2).
Example 53
Synthesis of Ru complex 4bh
The synthetic procedure for preparation of ligand 3bh is the same as in Example 1 in 5.0 mmol scale. 0.94g of yellow oil product 3bh was obtained (yield: 78%).
Ligand 3bh 1H NMR (CDC13, 400 MHz): δ 7.99 (s, 1H), 7.95-7.93 (m, 1H), 7.55-7.53 (d, 1H), 7.36-7.32 (m, 2H), 7.30-7.23 (m, 2H), 7.03-6.98 (m, 1H), 6.66-6.61 (m, 2H), 5.72-5.68 (m, 1H), 5.36-5.34 (m, 1H), 4.46-4.45 (d, 2H), 3.85 (s, 3H).
The procedure for preparation of Ru complex 4bh is the same as in Example 1 in 1.0 mmol scale. 542mg of green solid product 4bh was obtained (yield: 74%).
Ru complex (4bh) 1HNMR (400 MHz, CDC13): δ 18.89 (s, 1H, Ru=CH), 7.91-7.89 (d, J= 8.0 Hz, 1H), 7.76-7.74 (dd, J= 8.0, 1.5 Hz, 1H), 7.51-7.48 (td, J= 8.5, 7.0, 1.5 Hz, IH), 7.25-7.21(td, J= 13.5, 11.0, 2.0 Hz, IH), 7.19-7.16 (t, J= 8.0 Hz, IH), 7.12-7.09 (t, J= 7.5 Hz, 2H), 7.04-7.03 (d, J= 7.0 Hz, IH), 7.00-6.88 (m, 3H), 6.78-6.76 (d, J = 7.0 Hz, IH), 6.65 (brs, IH, H), 6.64-6.59 (t, J= 12.5 Hz, IH, NCH2), 4.08(brs, 2H, NCH2CH2N), 3.99 (brs, 2H, NCH2CH2N), 3.72-3.69 (dd, J= 13.5, 2.0 Hz, IH, NCH2), 3.67 (s, 3H, COOCH3), 2.62-2.03 (m, 18H).
Example 54
Synthesis of Ru complex 4bj
The synthetic procedure for preparation of ligand 3bj is the same as in Example 1 in 5.0 mmol scale. 0.99g of yellow oil product 3bj was obtained (yield: 82%).
Ligand 3bj 1H MR (CDC13, 400 MHz): δ 7.58-7.57 (d, IH), 7.38-7.36 (d, IH), 7.32-7.25 (m, 2H), 7.08-7.00 (m, 3H), 6.74-6.70 (m, IH), 6.65-6.63 (d, IH), 5.73-5.69 (m, IH), 5.33-5.30 (m, IH), 4.90 (s, IH), 4.35 (s, 2H), 2.63 (s, 6H).
The procedure for preparation of Ru complex 4bj is the same as in Example 1 in 1.0 mmol scale. 508mg of green solid product 4bj was obtained (yield: 69%).
Ru complex (4bj) 1HNMR (400 MHz, CDC13): δ 18.90 (s, IH, Ru=CH), 7.63-7.61 (d, J = 7.5 Hz, IH), 7.49-7.46 (t, J = 7.0 Hz, IH), 7.19-7.16 (t, J = 8.0 Hz, IH), 7.11-6.95 (m, 6H), 6.87-6.84 (t, J = 8.0 Hz, IH), 6.80-6.79 (d, J = 7.5 Hz, IH), 6.72 (brs, IH), 6.68-6.65 (d, J = 11.5 Hz, IH, NCH2), 5.50-5.45 (t, J = 13.0 Hz, IH, NCH2), 4.15-3.96 (m ,4H, NCH2CH2N), 3.51-3.48 (d, J = 13.5 Hz, IH, NH), 2.66-2.30 (m, 21H, aromatic CH3, NCH3), 2.05 (brs, 3H, NCH3).
Example 55
Synthesis of Ru complex 6a
SMl-5a (5.0mmol) and SM2-5a (5.0mmol) was added into a 50 mL of three-neck round-bottom flask filled with inert gas (Ar), and followed by adding anhydrous DCM (10 mL) and Na2S04 (5 eq) was added. The reaction was stirred until completed overnight (monitored by TLC). The reaction mixture was filtered, and the crude imine product 5a (1.25g, 97%) was obtained by removing all DCM solvent under vacuum. The crude imine product 5a was directly used for next step to prepare Ru complex 6a.
To a 50 mL two-necked round bottom flask, after filling with Ar atmosphere, were added ligand 5a (l .Ommol) and CuCl (3.0mmol, 3eq) and 30 mL dry DCM, followed by refilling with Ar three times and protected with Ar balloon in close system. Ru complex lb (l.Ommol) was added under Ar protection, and the mixture was stirred for 0.5 hr at room temperature.
After the reaction was complete, the solution was filtered and the filtrate was concentrated and slurred with silica gel. The crude was obtained by silica gel column chromatography and washed with methanol or pentane-DCM to obtain 453mg of yellow-green solid product 6a, yield: 79%.
Ru complex (6a) 1HNMR (400 MHz, CDC13): δ 18.53 (s, 1H, Ru=CH), 8.59 (s, 1H), 7.28-6.49 (m, 11H), 4.160 (s, 4H, NCH2CH2N), 2.50 (s, 12H), 2.42 (s, 6H).
Example 56
Synthesis of Ru complex 6b
The synthetic procedure for preparation of ligand 5b is the same as in Example 52 in 5.0 mmol scale. 1.21g of crude imine product 5b was obtained (yield: 95%), and it was directly used for next step to prepare Ru complex 6b.
To a 50 mL two-necked round bottom flask, after filling with Ar atmosphere, were added ligand 5b (l .Ommol) and CuCl (3.0mmol, 3eq) and 30 mL dry DCM, followed by refilling with Ar three times and protected with Ar balloon in close system. Ru complex la (l .Ommol) was added under Ar protection, and the mixture was stirred for 0.5 hr at room temperature.
After the reaction was complete, the solution was filtered and the filtrate was concentrated and slurred with silica gel. The crude was obtained by silica gel column chromatography and washed with methanol or pentane-DCM to obtain 414mg yello-green solid product 6b, yield: 77%.
Ru complex (6b) 1HNMR (400 MHz, CDC13): δ 19.20 (d, J = 10.8 Hz, Ru=CH), 8.82 (d, J = 9.2 Hz, 1H), 7.84 (m, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.45 (m, 4H), 2.46-1.29 (m, 33H, PCy3).
Example 57
Synthesis of Ru complex 6c
The synthetic procedure for preparation of ligand 5c is the same as in Example 52 in 5.0 mmol scale. 1.16g of crude imine product 5c was obtained (yield: 92%), and it was directly used for next step to prepare Ru complex 6c.
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 664 mg of yellow-green solid product 6c was obtained (96% yield).
Ru complex (6c) 1HNMR (400 MHz, CDC13): δ 18.52 (s, 1H, Ru=CH), 8.60(s, 1H), 7.28-7.13 (m, 7H), 7.02 (d, J = 8.8 Hz, 1H), 6.80 (m, 1H), 6.09 (d, J = 8.8 Hz, 1H), 4.16 (s, 4H, NCH2CH2N), 3.84 (s, 3H), 2.51 (m, 18H).
Example 58
Synthesis of Ru complex 6d
The synthetic procedure for preparation of ligand 5d is the same as in Example 52 in 5.0 mmol scale. 1.18g of crude imine product 5d was obtained (yield: 94%), and it was directly used for next step to prepare Ru complex 6d.
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 68 mg of yellow-green solid product 6d was obtained (31% yield).
Ru complex (6d): 1HNMR (400 MHz, CDC13): δ 18.73 (s, 1H, Ru=CH), 8.62 (s, 1H), 7.67-7.46 (m, 3H), 7.11 (s, 4H), 6.78-6.65 (m, 5H), 4.13 (s, 4H, NCH2CH2N), 3.81 (s, 3H), 2.49 (m, 18H).
Example 59
Synthesis of Ru complex 6e
The synthetic procedure for preparation of ligand 5e is the same as in Example 52 in 5.0 mmol scale. 1.13g of crude imine product 5e was obtained (yield: 93%), and it was directly used for next step to prepare Ru complex 6e.
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 41 mg of yellow-green solid product 6e was obtained (24% yield).
Ru complex (6e) 1HNMR (400 MHz, CDC13): δ 18.74 (s, 1H, Ru=CH), 8.60 (s, 1H), 7.69-7.49 (m, 3H), 7.12-7.04 (m, 8H), 6.80 (d, J = 8.7 Hz, 1H), 4.13 (s, 4H, NCH2CH2N), 2.50 (m, 18H).
Example 60
Synthesis of Ru complex 6f
The synthetic procedure for preparation of ligand 5f is the same as in Example 52 in 5.0 mmol scale. 1.28g of crude imine product 5f was obtained (yield: 94%), and it was directly used for next step to prepare Ru complex 6f .
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 664 mg of yellow-green solid product 6f was obtained (17% yield).
Ru complex (6f) 1HNMR (400 MHz, CDC13): δ 18.60 (s, 1H, Ru=CH), 8.58 (s, 1H), 7.48-7.29 (m, 2H), 7.02 (d, J = 8.8 Hz, 2H), 6.74-6.69 (m, 3H), 4.17 (s, 4H, NCH2CH2N), 3.85 (s, 3H), 2.52 (m, 18H).
Example 61
Synthesis of Ru complex 6g
The synthetic procedure for preparation of ligand 5g is the same as in Example 52 in 5.0 mmol scale. 1.23g of crude imine product 5g was obtained (yield: 96%), and it was directly used for next step to prepare Ru complex 6g.
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 35 mg of green solid product 6g was obtained (22% yield).
Ru complex (6g) 1H- MR (400 MHz, CDC13): δ 18.66 (s, 1H, Ru=CH), 8.56 (s, 1H), 7.50-7.34 (m, 2H), 7.26 (s, 4H), 7.00-6.40 (m, 5H), 4.14 (s, 4H, NCH2CH2N), 3.81 (s, 3H), 2.49 (m, 18H).
Example 62
Synthesis of Ru complex 6h
The synthetic procedure for preparation of ligand 5h is the same as in Example 52 in 5.0 mmol scale. 1.29g of crude imine product 5h was obtained (yield: 96%), and it was directly used for next step to prepare Ru complex 6h.
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 106 mg of yellow-green solid product 6h was obtained (37% yield).
Ru complex (6h) 1HNMR (400 MHz, CDC13): δ 16.52 (s, 1H, Ru=CH), 8.43 (s,
1H, N=CH), 8.10 (s, 1H), 7.46-7.22 (m, 2H), 7.73-6.96 (m, 8H), 4.19 (s, 4H, NCH2CH2N), 3.95 (s, 3H), 3.87 (s, 3H), 2.49 (s, 12H), 2.48 (s, 6H).
Example 63
Synthesis of Ru complex 6j
The synthetic procedure for preparation of ligand 5j is the same as in Example 52 in 5.0 mmol scale. 1.3 lg of crude imine product 5j was obtained (yield: 97%), and it was directly used for next step to prepare Ru complex 6j .
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 190 mg of red solid product 6j was obtained, and the product 6j is unstable and difficult to detect the structure by 1HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction.
Example 64
Synthesis of Ru complex 8a
The synthetic procedure for preparation of ligand 7a is the same as in Example 1 in 5.0 mmol scale. 0.26g of oily product 7a was obtained (yield: 28%).
Ligand 7a 1H- MR (400 MHz, CDC13): δ 7.21 (dd, J= 18.0, 11.20 Hz, 1H), 7.00 (td, J = 9.2, 2.8, 1.6 Hz, 1H), 6.73-6.67 (m, 1H), 5.67 (dd, J = 18.0, 1.2 Hz, 1H), 5.34 (d, J= 11.2 Hz, 1H), 2.77 (d, J= 2.4 Hz, 6H).
The procedure for preparation of Ru complex 8a is the same as in Example 1 in 1.0 mmol scale. 208 mg of green solid product 8a was obtained, yield: 32%.
Ru complex (8a) 1HNMR (400 MHz, CDC13): 516.80 (s, 1H, Ru=CH), 7.07 (s, 4H, aromatic H), 6.94 (m, 1H), 6.30 (d, J = 6.4 Hz, 1H), 4.11 (s, 4H, NCH2CH2N), 2.69 (s, 6H), 2.49 (s, (s, 12H), 2.42 (s, 6H).
Example 65
Synthesis of Ru complex 8b
The synthetic procedure for preparation of ligand 7b is the same as in Example 1 in 5.0 mmol scale. 0.89g of solid product 7b was obtained (yield: 92%).
Ligand 7b 1H- MR (400 MHz, CDC13): δ 8.25 (d, J = 2.7 Hz, 1H), 8.05 (dd, J = 8.7 Hz, 2.4 Hz, 1H), 6.90 (d, J = 9.0 Hz, 1H), 6.82 (dd, J = 17.4, 11.1 Hz, 1H), 5.77 (dd, J= 17.7, 0.9 Hz, 1H), 5.37 (dd, J= 10.8, 0.6 Hz, 1H), 2.92 (s, 6H).
The procedure for preparation of Ru complex 8b is the same as in Example 1 in 1.0 mmol scale. 59 mg of green solid product 8b was obtained (yield: 9%).
Ru complex (8b) 1HNMR (400 MHz, CDC13): δ 16.97 (s, 1H, Ru=CH), 8.40 (dd, J = 8.8, 2.4 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.29 (d, J = 8.8 Hz, 1H), 7.07 (s, 4H), 4.20 (s, 4H, NCH2CH2N), 2.57 (s, 6H), 2.47 (s, 12H), 2.39 (s, 6H).
Example 66
Synthesis of Ru complex 8c
The synthetic procedure for preparation of ligand 7c is the same as in Example 1 in 5.0 mmol scale. 0.96g of yellow oil product 7c was obtained (yield: 96%).
Ligand 7c 1H- MR (400 MHz, CDC13): δ 8.19 (d, J = 2.8 Hz, 1H), 7.98 (dd, J =9.0, 2.8 Hz, 1H), 6.86 (d, J = 9.0 Hz, 1H), 6.73 (dd, J = 17.6 Hz, 11.2 Hz, 1H), 5.69 (d, J= 17.6 Hz, 1H), 5.29 (d, J = 11.2 Hz, 1H), 3.12 (q, 2H, J = 6.8 Hz), 2.78 (s, 3H), 1.09 (t, J= 6.8 Hz, 3H).
The procedure for preparation of Ru complex 8c is the same as in Example 1 in 1.0 mmol scale. 161 mg of green solid product 8c was obtained (24% yield).
Ru complex (8c) 1HNMR (400 MHz, CDC13): δ 16.69 (s, 1H, Ru=CH), 8.36 (dd, J = 8.8, 2.4 Hz, 1H), 7.62 (d, J = 2.4 Hz, 1H), 7.18 (d, J = 8.8 Hz, 1H), 7.17-7.00 (m, 4H), 4.16-3.80 (m, 6H), 2.84-2.08 (m, 21H), 0.57 (t, J= 6.8 Hz, 3H). Example 67
Synthesis of Ru complex 8d
The synthetic procedure for preparation of ligand 7d is the same as in Example 1 in 5.0 mmol scale. 1.02g of yellow oil product 7d was obtained (yield: 92%).
Ligand 7d 1H NMR(400 MHz, CDC13): 8.27(d, J = 2.7 Hz, 1H), 8.05 (dd, J =
9.0, 3.0 Hz, 1H),6.92 (d, J= 9.0 Hz, 1H), 6.75 (dd, J= 18.0, 10.8 Hz, 1H), 5.77 (dd, J = 17.7, 0.9 Hz, 1H), 5.34 (dd, J = 1.2 Hz, 10.8 Hz, 1H),3.71 (m, 1H), 2.74 (s, 3H), 1.13 (d, J= 6.6 Hz, 6H).
The procedure for preparation of Ru complex 8d is the same as in Example 1 in 1.0 mmol scale. 103mg green solid product 8d was obtained, yield: 15%.
The product is unstable, so it is difficult to detect the structure by 1HNMR. But the crude Ru complex 8d could be directly used for metathesis reaction.
Example 68
Synthesis of Ru complex 8e
The synthetic procedure for preparation of ligand 7e is the same as in Example 1 in 5.0 mmol scale. 0.63g of yellow oil product 7e was obtained (yield: 37%).
Ligand 7e 1H-NMR (400 MHz, CDC13): δ 8.11-8.06 (m, 2H, aromatic H), 6.65-6.55 (m, 2H, aromatic H, CH=CH2), 5.61 (d, J= 17.1 Hz, CH=CH2), 5.47 (d, J = 10.8 Hz, CH=CH2), 4.43 (s, 1H, NH), 3.78-3.74 (m, 1H, NCH), 1.28 (d, J = 7.8 Hz, NCH(CH3)2).
The procedure for preparation of Ru complex 8e is the same as in Example 1 in 1.0 mmol scale. 74mg green solid product 8e was obtained, yield: 15%.
The product is unstable, so it is difficult to detect the structure by 1HNMR. But the crude Ru complex 8e could be directly used for metathesis reaction.
Example 69
Synthesis of Ru complex 8f
The synthetic procedure for preparation of ligand 7f is the same as in Example 1 in 5.0 mmol scale. 0.68g of yellow oil product 7f was obtained (yield: 66%).
Ligand 7f 1HNMR (400 MHz, CDC13): δ 8.11 (d, J = 2.0 Hz, 1H), 7.89 (dd, J = 8.8, 2.0 Hz, 1H), 6.96 (d, J= 8.8 Hz, 1H), 6.91 (dd, J= 12.0, 18.4 Hz, 1H), 5.76 (dd, J = 18.40, 1.20 Hz, 1H), 5.31 (dd, J= 12.0, 1.2 Hz, 1H), 3.90 (s, 3H), 2.83 (s, 6H).
The procedure for preparation of Ru complex 8f is the same as in Example 1 in 1.0 mmol scale. 396 mg of green solid product 8f was obtained (yield: 59%).
Ru complex (8f) 1HNMR (400 MHz, CDC13): 516.80 (s, 1H, Ru=CH), 8.18 (dd, J = 8.8, 2.4 Hz, 1H), 7.46 (d, J = 2.4 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H), 7.07 (s, 4H), 4.11 (s, 4H, NCH2CH2N), 3.91 (s, 3H), 2.58 (s, 6H), 2.47 (s, 12H), 2.43 (s, 6H).
Example 70
Synthesis of Ru complex 8g
The synthetic procedure for preparation of ligand 7g is the same as in Example 1 in 5.0 mmol scale. 1.03g of yellow oil product 7g was obtained (yield: 96%).
Ligand 7g 1H MR (CDC13, 400Hz): δ 7.45-7.44 (m, 1H), 7.25-7.21 (m, 1H), 7.12-7.10 (m, 1H), 7.05-6.99 (m, 2H), 5.69-5.65 (m, 1H), 5.27-5.25 (m, 1H),3.80 (s, 2H), 3.70 (s, 3H), 2.90 (s, 3H).
The procedure for preparation of Ru complex 8g is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8g was obtained (yield: 79%).
Ru complex (8g) 1HNMR (400 MHz, CDC13): δ 16.70 (s, 1H, Ru=CH), 7.37 (m, 1H), 7.04-6.91 (m, 6H), 6.72 (d, J= 7.6 Hz, 1H), 5.05 (d, J = 11.6 Hz, 1H), 3.88-3.85 (m, 4H, NCH2CH2N), 3.52 (s, 3H), 3.44 (d, J= 11.6 Hz, 1H), 2.85-1.50 (m, 21H).
Example 71
Synthesis of Ru complex 8h
The synthetic procedure for preparation of ligand 7h is the same as in Example 1 in 5.0 mmol scale. 0.64g of product 7h was obtained (yield: 51%). The product 7h is confirmed by LC-MS (M+H+): m/z calculated: 251.2, found: 251.2, and directly used for preparation of the Ru complex 8h. The procedure for preparation of Ru complex 8h is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8h was obtained (yield: 74%).
Ru complex (8h) 1HNMR (400 MHz, CDC13): δ 16.56 (s, 1H, Ru=CH), 8.33 (dd, J= 8.4, 2.4 Hz, 1H), 7.56 (d, J= 2.4 Hz), 7.20-6.94 (m, 5H), 5.22 (d, J= 11.2 Hz, 1H), 4.21-3.96 (m, 4H, NCH2CH2N), 3.56 (s, 3H), 3.54 (d, J= 11.2 Hz, 1H), 2.94-0.92 (m, 21H).
Example 72
Synthesis of Ru complex 8j
The synthetic procedure for preparation of ligand 7j is the same as in Example 1 in 5.0 mmol scale. 0.58g of yellow oil product 7j was obtained (yield: 46%).
Ligand 7j 1HNMR (400 MHz, CDC13): δ 8.24 (d, J = 2.8 Hz, 1H), 8.08 (dd, J =
8.8, 2.8 Hz, 1H), 7.03 (d, J = 8.8 Hz, 1H), 6.79 (dd, J = 17.6, 10.8 Hz, 1H), 5.79
(dd, J = 17.6, 1.2 Hz, 1H), 5.4 (dd, J = 10.8, 1.2 Hz, 1H), 5.05 (m, 1H), 3.94 (s, 2H), 3.024 (s, 3H), 1.24 (d, J = 6.4 Hz, 6H).
The procedure for preparation of Ru complex 8j is the same as in Example 1 in 1.0 mmol scale. 320 mg of green solid product 8j was obtained (yield: 43%).
Ru complex (8j) 1HNMR (400 MHz, CDC13): δ 16.64 (s, 1H, Ru=CH), 8.34 (dd, J= 8.4, 2.4 Hz, 1H), 7.54 (d, J= 2.4 Hz, 1H), 7.25-6.93 (m, 5H), 5.17 (d, J= 11.2 Hz, 1H), 4.84-4.83 (m, 1H), 4.14-3.93 (m, 4H, NCH2CH2N), 3.45 (d, J = 11.2 Hz, 1H), 2.89-1.19 (m, 27 H).
Example 73
Synthesis of Ru complex 8k
The synthetic procedure for preparation of ligand 7k is the same as in Example 1 in 5.0 mmol scale. 0.53g of product 7k was obtained (yield: 44%). The product 7k is confirmed by LC-MS (M+H+): m/z calculated: 251.2, found: 251.2, and directly used for preparation of the Ru complex 8k.
The procedure for preparation of Ru complex 8k is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8k was obtained (yield: 74%).
Ru complex (8k) 1HNMR (400MHz, CDC13): δ 16.70 (s, 1H, Ru=CH),
7.18- 7.13 (m, 3H), 7.05 (s, 1H), 6.96-6.94 (m, 2H), 6.48-6.45 (dd, J=8.0, 2.0 Hz, 1H),
5.19- 5.16 (d, J=15.5 Hz, 1H), 4.17 (s, 2H), 3.94 (s, 2H), 3.62 (s, 3H), 3.50-3.47 (d, J=15.5 Hz, 1H), 2.94 (s, 3H), 2.80 (s, 3H), 2.49 (s, 3H), 2.32 (s, 6H), 2.00 (s, 6H).
Example 74
Synthesis of Ru complex 8m
The synthetic procedure for preparation of ligand 7m is the same as in Example 1 in 5.0 mmol scale. 0.76g of yellow oil product 7m was obtained (yield: 68%).
Ligand 7m 1H- MR (CDC13, 400Hz): δ 7.15-7.13 (m, 1H), 7.11-7.08 (m, 1H), 7.05-6.99 (m, 1H), 6.93-6.89 (m, 1H), 5.68-5.65 (m, 1H), 5.32-5.30 (d, 1H), 3.74 (s, 2H), 3.69 (s, 3H), 2.86 (s, 3H).
The procedure for preparation of Ru complex 8m is the same as in Example 1 in 1.0 mmol scale. 430 mg of green solid product 8m was obtained (yield: 41%).
Ru complex (8m) 1HNMR (400MHz, CDC13): δ 16.67 (s, 1H, Ru=CH), 7.10-7.16 (m, 3H), 7.02 (s, 1H), 6.91-6.94 (m, 2H), 6.43-6.45 (dd, J=8.75,2.5 Hz, 1H), 5.13-5.16 (d, J=15.5 Hz, 1H), 4.15 (s, 2H), 3.91(s, 2H), 3.59 (s, 3H), 3.44-3.47 (d, J=15.0 Hz, 1H), 2.92 (s, 3H), 2.77(s, 3H), 2.47 (s, 3H), 2.29 (s, 6H), 1.97 (s, 6H)..
Example 75
Synthesis of Ru complex 8n
The synthetic procedure for preparation of ligand 7n is the same as in Example 1 in 5.0 mmol scale. 0.79g of yellow oil product 7n was obtained (yield: 71%).
Ligand 7n 1H- MR (400 MHz, CDC13): δ 7.02 (dd, J = 9.6, 3.2 Hz, 1H), 6.87 (td, J = 8.8, 3.2 Hz, 1H), 6.79 (dd, , J = 17.2, 11.2 Hz, 1H), 6.43 (dd, J = 8.8, 4.8 Hz, 1H), 5.65 (dd, J = 17.2, 1.6 Hz, 1H), 5.39 (dd, J = 11.2, 1.6 Hz, 1H), 5.11 (m, 1H), 3.85 (s, 2H), 1.27 (d, J= 6.4 Hz, 6H).
The procedure for preparation of Ru complex 8n is the same as in Example 1 in 1.0 mmol scale. 599 mg of green solid product 8n was obtained (yield: 87%).
Ru complex (8n) 1HNMR (400 MHz, CDC13): 516.82 (s, 1H, Ru=CH), 7.12-7.02 (m, 5H), 6.64 (m, 1H), 6.51-6.48 (m, 1H), 4.15 (s, 4H, NCH2CH2N), 3.95-3.92 (m, 1H), 3.74 (s, 3H), 2.50-2.37 (m, 18H), 0.96 (d, J= 6.4 Hz, 1H).
Example 76
Synthesis of Ru complex 8p
The synthetic procedure for preparation of ligand 7p is the same as in Example 1 in 5.0 mmol scale. 0.365g of product 7p was obtained (yield: 27%).
Ligand 7p 1H- MR (400 MHz, CDC13): δ 7.42 (m, 1H), 7.17-7.15 (m, 1H), 7.09-7.06 (m, 1H), 7.04-6.98 (m, 1H), 5.69-5.65 (m, 1H), 5.30-5.27 (m, 1H), 5.0-4.95 (m, 1H), 3.75 (s, 2H), 3.23-3.19 (m, 2H), 1.19-1.18 (d, 6H), 1.07-1.04 (m, 3H).
The procedure for preparation of Ru complex 8p is the same as in Example 1 in
1.0 mmol scale. 167 mg of green solid product 8p was obtained (yield: 23%).
Ru complex (8p) 1HNMR (400 MHz, CDC13): 516.52 (s, 1H, Ru=CH), 7.34-32 (dd, J= 8.5, 2.0 Hz, 1H), 7.17 (s, 1H), 7.08 (s, 1H), 7.03 (s, 1H), 6.93 (s, 1H), 6.79-6.77 (d, J= 8.0 Hz, 1H), 6.66 (s, 1H), 5.08-5.05 (d, J= 14.5 Hz, 1H), 4.81-4.76 (m, 1H), 4.16 (s, 2H, NCH2CH2N), 3.90 (s, 2H, NCH2CH2N), 3.62-3.59 (d, J= 16.0 Hz, 1H, NCH2), 2.91 (s, 3H), 2.81 (s, 3H), 2.48 (s, 3H), 2.32 (s, 3H), 2.30 (s, 3H), 2.16-2.09 (m, 2H, NCH2CH3), 1.95 (s, 3H), 1.24-1.19 (dd, J= 17.5, 6.0 Hz, 6H, OCH(CH3)2), 0.53-0.50 (t, J= 5.5 Hz, 3H, NCH2CH3).
Example 77
Synthesis of Ru complex 8q
The synthetic procedure for preparation of ligand 7q is the same as in Example 1 in 5.0 mmol scale. 487mg of yellow oil product 7q was obtained (yield: 38%).
Ligand 7q 1H- MR (400 MHz, CDC13): δ 7.29-7.26 (m, 1H), 7.17-7.14 (m, 1H), 6.85-6.14 (m, 2H), 6.56-6.55 (d, 1H), 5.65-5.62 (m, 1H), 5..37-5.30 (m, 1H), 4.19-4.15 (m, 1H), 3.74 (s, 3H), 1.57-1.50 (d, 3H). The procedure for preparation of Ru complex 8q is the same as in Example 1 in 1.0 mmol scale. 147mg of brown solid product 8q was obtained (yield: 21%).
Ru complex (8q) 1HNMR (400 MHz, CDC13): 516.91 (s, 1H, Ru=CH), 7.43-7.40 (m, 1H), 7.08-7.03 (m, 5H), 6.85-6.84 (d, J = 6.5 Hz, 1H), 6.72-6.70 (d, J = 7.5 Hz, 1H), 4.12 (s, 4H, NCH2CH2N), 4.07 (s, 1H, H), 4.02-3.98 (m, 1H, NCH), 3.76 (s, 3H, COOCH3), 2.52 (s, 9H), 2.39 (brs, 9H), 1.02-1.01 (d, J = 6.0 Hz, 3H)
Example 78
Synthesis of Ru complex 8r
The synthetic procedure for preparation of ligand 7r is the same as in Example 1 in 5.0 mmol scale. 1.06g of yellow oil product 7r was obtained (yield: 83%). The product 7r is confirmed by LC-MS (M+H+): m/z calculated: 285.1, found: 285.1, and directly used for preparation of Ru complex 8r..
The synthetic procedure for preparation of Ru complex 8r is the same as in
Example 1 in 1.0 mmol scale. 386 mg of brown solid product 8r was obtained by precipitation in hexane and MeOH, and the crude product 8r is unstable and difficult to detect the structure by 1HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction.
Example 79
Synthesis of Ru complex 8s
The synthetic procedure for preparation of ligand 7s is the same as in Example 1 in 5.0 mmol scale. 1.18g of yellow oil product 7s was obtained (yield: 67%).
Ligand 7s 1H- MR (400 MHz, CDC13): δ 7.44 (d, J = 2.7Hz, 1H, aromatic H), 7.64 (d, J = 3.0 Hz, 1H, aromatic H), 7.16-7.12 (m, 2H, aromatic H), 7.08-6.92 (m, 2H, aromatic H, CH=CH2), 6.76 (d, J = 8.7 Hz, 1H, aromatic H), 5.66 (dd, J = 17.7, 1.5Hz, 1H, CH=CH2), 5.25 (dd, J = 10.8, 0.9 Hz, 1H, CH=CH2), 4.46 (t, J = 6.0 Hz, 1H, OCH), 4.06 (s, 2H, NCH2), 2.63 (d, J = 8.4 Hz, 3H, NCH3), 1.31-1.26 (m, 6H, OCH(CH3)2).
The procedure for preparation of Ru complex 8s is the same as in Example 1 in 1.0 mmol scale. 379 mg of green solid product 8s was obtained (yield: 48%).
Ru complex (8s) 1HNMR (400 MHz, CDC13): 517.58 (d, J = 6.0 Hz, 1H, Ru=CH), 7.59-7.55 (m, 2H), 7.48 (d, J = 8.4 Hz, 1H), 7.22 (dd, J = 2.4, 8.8 Hz, 1H), 7.14 (d, J= 8.4 Hz, 1H), 6.78 (d, J= 8.8 Hz, 1H), 4.80 (d, J= 12.8 Hz, 1H), 4.50-4.47 (m, 1H), 4.05 (d, J= 12.8 Hz, 1H), 2.704 (s, 3H), 2.38-0.78 (m, 39H, PCy3).
Example 80
Synthesis of Ru complex 8t
The synthetic procedure for preparation of ligand 7t is the same as in Example 1 in 5.0 mmol scale. 0.83g of product 7t was obtained (yield: 51%). The product 7q is confirmed by LC-MS (M+H+): m/z calculated: 316.1, found: 316.1, and directly used for preparation of the Ru complex 8t.
The procedure for preparation of Ru complex 8t is the same as in Example 1 in
1.0 mmol scale. 602 mg of green solid product 8t was obtained (yield: 77%).
Ru complex (8t) 1HNMR (400 MHz, CDC13): 516.87 (s, 1H, Ru=CH), 7.41 (dd,
7 = 2, 8.4 Hz, 1H), 7.19-7.13 (m, 5H), 7.031 (d, 7 = 8.4 Hz, 1H), 6.93 (d, 7 = 7.2 Hz,
1H), 6.77-6.76 (m, 2H), 6.65 (t, 7 = 7.2 Hz, 1H), 4.66 (d, 7 = 12.4 Hz, 1H), 4.48-4.43
(m, 1H), 4.02-3.98 (m, 5H), 2.54-2.30 (m, 18H), 2.25 (s, 3H), 1.29 (d, 7= 6 Hz, 6H). Example 81
Synthesis of Ru complex 8u
The synthetic procedure for preparation of ligand 7u is the same as in Example 1 in 5.0 mmol scale. 1.21g of yellow oil product 7u was obtained (yield: 71%).
Ligand 7u 1H- MR (400 MHz, CDC13): 5 7.44 (d, J = 2.7Hz, 1H, aromatic H), 7.64 (d, J = 3.0 Hz, 1H, aromatic H), 7.16-7.12 (m, 2H, aromatic H), 7.08-6.92 (m, 2H, aromatic H, CH=CH2), 6.76 (d, J = 8.7 Hz, 1H, aromatic H), 5.66 (dd, J = 17.7, 1.5Hz, 1H, CH=CH2), 5.25 (dd, J = 10.8, 0.9 Hz, 1H, CH=CH2), 4.46 (t, J = 6.0 Hz, 1H, OCH), 4.06 (s, 2H, NCH2), 2.63 (d, J = 8.4 Hz, 3H, NCH3), 1.31-1.26 (m, 6H, OCH(CH3)2). The procedure for preparation of Ru complex 8u is the same as in Example 1 in 1.0 mmol scale. 302 mg of green solid product 8u was obtained (yield: 37%).
Ru complex (8u) 1HNMR (400 MHz, CDC13): 516.84 (s, 1H, Ru=CH), 7.18 (d, J = 8.4 Hz, 1H), 7.81 (m, 5H), 6.75 (m, 1H), 6.62 (d, J = 8.8 Hz, 1H), 6.32 (d, J = 8.4 Hz, 1H), 4.29-4.24 (m, 1H), 4.11 (s, 4H, NCH2CH2N), 3.85 (d, J= 14.0 Hz, 1H), 3.09 (d, J= 14.0 Hz, 1H), 2.74 (s, 3H), 2.43-2.28 (m, 18H), 1.10 (d, J= 6.0 Hz, 6H).
Example 82
Synthesis of Ru complex 10a
The synthetic procedure for preparation of ligand 9a is the same as in Example 1 in 5.0 mmol scale. 0.97g of yellow oil product 9a was obtained (yield: 93%).
Ligand 9a 1H- MR (400 MHz, CDC13): δ 7.80 (dd, J= 8.4, 5.7 Hz, 1H), 7.38 (dd, J = 17.7, 11.1 Hz, 1H), 7.14 (dd, J = 10.5, 2.7 Hz, 1H), 6.90 (td, J = 8.4, 2.1 Ηζ, ΙΗ), 5.55 (d, J= 17.7 Hz, 1H), 5.30 (d, J= 11.1 Hz, 1H), 5.17-5.09 (m, lH), 1.27 (d, J= 6.3 Hz, 6H). The procedure for preparation of Ru complex 10a is the same as in Example 1 in
1.0 mmol scale. 128 mg of green solid product 10a was obtained (yield: 19%). The product is unstable, so it is difficult to detect the structure by 1HNMR. But the crude Ru complex 10a could be directly used for metathesis reaction. Example 83
Synthesis of Ru complex 10b
The synthetic procedure for preparation of ligand 9b is the same as in Example 1 in 5.0 mmol scale. 0.89g of yellow oil product 9b was obtained (yield: 87%).
Ligand 9b 1H- MR (400 MHz, CDC13): δ 7.80 (dd, J= 8.4, 5.7 Hz, 1H), 7.38 (dd, J = 17.7, 11.1 Hz, 1H), 7.14 (dd, J = 10.5, 2.7 Hz, 1H), 6.90 (td, J = 8.4, 2.1 Ηζ, ΙΗ), 5.55 (d, J= 17.7 Hz, 1H), 5.30 (d, J= 11.1 Hz, 1H), 5.17-5.09 (m, lH), 1.27 (d, J= 6.3 Hz, 6H).
The procedure for preparation of Ru complex 10b is the same as in Example 1 in 1.0 mmol scale. 97 mg of green solid product 10b was obtained (yield: 15%). The product is unstable, so it is difficult to detect the structure by 1HNMR. But the crude Ru complex 10b could be directly used for metathesis reaction.
Example 84
Synthesis of Ru complex 10c
The synthetic procedure for preparation of ligand 9c is the same as in Example 1 in 5.0 mmol scale. 0.82g of product 9c was obtained (yield: 76%). The product 9c is confirmed by LC-MS (M+H+): m/z calculated: 208.1, found: 208.0, and directly used for preparation of the Ru complex 10c.
The procedure for preparation of Ru complex 10c is the same as in Example 1 in
1.0 mmol scale. 29 mg of green solid product 10c was obtained (yield: 5%).
Ru complex (10c) 1HNMR (400 MHz, CDC13): δ 18.68 (s, 1H, Ru=CH), 8.44 (dd, J = 8.4, 2.4 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.60 (d, J = 2.4 Hz, 1H), 7.13 (s, 4H), 4.14 (s, 4H, NCH2CH2N), 3.97 (s, 3H), 2.48 (s, 12H), 2.459 (s, 6H).
Example 85
Synthesis of Ru complex lOd
The synthetic procedure for preparation of ligand 9d is the same as in Example 1 in 5.0 mmol scale. 0.78g of product 9d was obtained (yield: 72%). The product 9d is confirmed by LC-MS (M+H+): m/z calculated: 236.1, found: 236.1, and directly used for preparation of the Ru complex lOd.
The procedure for preparation of Ru complex lOd is the same as in Example 1 in 1.0 mmol scale. 238 mg of green solid product lOd was obtained (yield: 34%).
Ru complex (lOd) 1HNMR (400 MHz, CDC13): δ 18.71 (s, 1H, Ru=CH), 8.42 (dd, J = 9.0, 2.4 Hz, 1H), 8.18 (d, J = 9.0 Hz, 1H), 7.60 (d, J = 2.4 Hz, 1H), 7.13 (s, 4H), 5.25 (m, 1H), 4.13 (s, 4H, NCH2CH2N), 2.46 (m, 18H), 1.24 (d, J= 6.0 Hz, 6H,).
Example 86
Synthesis of Ru complex lOe
The synthetic procedure for preparation of ligand 9e is the same as in Example 1 in 5.0 mmol scale. 0.92g of product 9e was obtained (yield: 82%). The product 9e is confirmed by LC-MS (M+H+): m/z calculated: 225.1, found: 225.1, and directly used for preparation of the Ru complex lOe.
The procedure for preparation of Ru complex lOe is the same as in Example 1 in 1.0 mmol scale. 235 mg of green solid product lOe was obtained (yield: 34%).
Ru complex (lOe) 1HNMR (400 MHz, CDC13): δ 18.56 (s, 1H, Ru=CH), 7.98 (d, J =8.8 Hz, 1H), 8.18 (dd, J = 8.8, 2.4 Hz, 1H), 7.11 (s, 4H), 7.06 (d, J = 2.4 Hz, 1H), 5.23 (m, 1H), 4.11 (s, 4H, NCH2CH2N), 2.45 (m, 18H), 1.28 (d, J= 6.0 Hz, 6H). Example 87
Synthesis of Ru complex lOf
The synthetic procedure for preparation of ligand 9f is the same as in Example 1 in 5.0 mmol scale. 1.13g of yellow oil product 9f was obtained (yield: 81%).
Ligand 9f 1H- MR (400 MHz, CDC13): δ 7.52 (d, J = 3.0 Hz, 1H), 7.26 (dd, J = 8.7Hz, 3.0 Hz, 1H), 6.89 (d, J = 8.7 Hz, 1H), 5.75 (m, 1H), 5.21 (m, 1H), 5.07-4.97 (m, 2H), 3.17-3.16 (m, 2H), 2.82 (s, 3H), 2.35-2.28 (m, 2H), 1.35 (d, J= 6.0Hz, 6H).
The procedure for preparation of Ru complex lOf is the same as in Example 1 in 1.0 mmol scale. 274 mg of green solid product lOf was obtained (yield: 37%).
Ru complex (lOf) 1HNMR (400 MHz, CDC13): 1H- MR (400 MHz, CDC13): δ 18.74 (s, 1H, Ru=CH), 8.21 (dd, J= 8.0, 2.4 Hz, 1H), 8.08 (d, J= 8.0 Hz, 1H), 7.54 (d, J = 2.4 Hz, 1H), 7.12 (s, 4H), 5.32 (m, 1H), 5.25 (m, 1H), 4.13 (s, 4H, NCH2CH2N), 2.47 (m, 18H), 1.43 (d, J= 6.0 Hz), 1.24 (d, J= 6.0 Hz, 6H).
Example 88
Synthesis of Ru complex lOg
The synthetic procedure for preparation of ligand 9g is the same as in Example 1 in 5.0 mmol scale. 1.43g of yellow oil product 9g was obtained (yield: 79%).
Ligand 9g 1H- MR (400 MHz, CDC13): δ 7.88 (d, J = 9.6 Hz, 1H, aromatic H), 7.86-7.21 (m, 5H, aromatic H, CH=CH2), 6.83 (d, J = 9.3 Hz, 1H, aromatic H), 5.68 (d, J = 16.8 Hz, 1H, CH=CH2), 5.40 (d, J = 11.1 Hz, 1H, CH=CH2), 5.32 (s, 2H, OCH2), 4.55 (m, 1H, OCH(CH3)2), 1.31 (d, J= 8.1 Hz, 6H, OCH(CH3)2).
The procedure for preparation of Ru complex lOg is the same as in Example 1 in 1.0 mmol scale. 440 mg of green solid product lOg was obtained (yield: 53%).
Ru complex (lOg) 1HNMR (400 MHz, CDC13): δ 18.60 (s, 1H, Ru=CH), 8.01 (d,
J =8.4 Hz, 1H), 7.59 (dd, J = 1.6, 8.4 Hz, 1H), 7.31-7.23 (m, 1H), 7.24 (dd, J = 2.8, 8.8 Hz, 1H), 6.81 (d, J =8.8 Hz, 1H), 6.71 (d, J = 2.0 Hz, 1H), 5.33 (s, 2H), 4.52 (m, 1H), 4.16 (s, 4H, NCH2CH2N), 2.51 (s, 12H), 2.48 (s, 6H), 1.28 (d, 6H, J= 6.0 Hz). Example 89
Synthesis of Ru complex lOh
The synthetic procedure for preparation of ligand 9h is the same as in Example 1 in 5.0 mmol scale. 1.38g of yellow oil product 9h was obtained (yield: 83%).
Ligand 9h 1H- MR (400 MHz, CDC13): δ 7.87 (d, J = 8.4 Hz, 1H, aromatic H), 7.55-7.24 (m, 6H, aromatic H, CH=CH2), 6.95-6.90 (m, 1H, aromatic H), 5.66 (d, J = 21.6 Hz, 1H, CH=CH2), 5.42-5.32 (m, 3H, CH=CH2, OCH2), 4.60 (m, 1H, OCH(CH3)2), 1.25 (d, J= 8.1 Hz, 6H, OCH(CH3)2).
The procedure for preparation of Ru complex lOh is the same as in Example 1 in 1.0 mmol scale. 183 mg of green solid product lOh was obtained (yield: 23%).
Ru complex (lOh) 1HNMR (400 MHz, CDC13): δ 18.60 (s, 1H, Ru=CH), 8.00 (d,
J =8.8 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.32-7.29 (m, 1H), 7.14 (s, 4H), 7.01-6.70 (m, 4H), 5.38 (s, 2H), 4.56 (m, 1H), 4.16 (s, 4H, NCH2CH2N), 2.71 (s, 12H), 2.52 (s, 6H), 1.32 (d, J= 6.0 Hz, 6H). Example 90
Synthesis of Ru complex lOj
The synthetic procedure for preparation of ligand 9j is the same as in Example 1 in 5.0 mmol scale.1.19g of yellow oil product 9j was obtained (yield: 63%).
Ligand 9j 1H- MR (300 MHz, CDC13): δ 8.42 (d, J = 2.1 Hz, 1H, aromatic H), 8.14 (d, J = 2.1 Hz, IH, aromatic H), 8.11 (d, J = 2.4 Hz, IH, aromatic H), 7.48-7.24 (m, 3H, aromatic H, CH=CH2), 6.84 (d, J= 9.0 Hz, IH, aromatic H), 5.84 (d, J= 17.7 Hz, IH, CH=CH2), 5.53 (d, J = 10.8 Hz, IH, CH=CH2), 5.37 (s, 2H, OCH2), 4.57 (m, IH, OCH(CH3)2), 1.32 (d, J= 8.1 Hz, 6H, OCH(CH3)2). The procedure for preparation of Ru complex lOj is the same as in Example 1 in
1.0 mmol scale. 345 mg of yellow solid product lOj was obtained (yield: 41%).
It is confirmed byRu complex (lOj) 1HNMR (400 MHz, CDC13): δ 18.75 (s, IH, Ru=CH), 8.45 (dd, J =8.8, 1.6 Hz, IH), 8.21 (d, J =8.8 Hz, IH), 7.64 (d, J =1.6 Hz, IH), 7.39-7.25 (m, 2H), 7.17 (s, 4H), 6.83 (d, J =8.8 Hz, IH), 5.37 (s, 2H), 4.53 (m, IH), 4.15 (s, 4H, NCH2CH2N), 2.51 (m, 18H), 1.40 (d, J= 6.0 Hz, 6H).
Example 91
Synthesis of Ru complex 11a
The Ru complex (Grela catalyst 2f, l .Ommol) and 4-chlorin pyridine ligand (lOmmol) were reacted directly to form another Ru complex 11a in 20 mL of anhydrous DCM in a 100 mL of three-neck flask filled with inert gas (Ar), and the reaction mixture was stirred for 0.5 hr at room temperature. After complete, 20mL of pentane (-10°C) was added into reaction solution, then filtered and washed with MeOH to obtain 747 mg of yellow-green solid product 11a, yield: 95%.
Ru complex (11a) 1HNMR (400 MHz, CDC13): δ 17.00 (s, IH), 8.47-6.83 (m,
11H), 4.91 (m, IH), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J= 4.4 Hz, 6H).
Example 92
Synthesis of Ru complex lib
The synthetic procedure is the same as in Example 85. 394 mg of yellow-green solid product lib was obtained (yield: 48%).
Ru complex (lib) 1HNMR (400 MHz, CDC13): δ 16.49 (s, IH), 8.90-8.50 (m, 2H), 7.86 (d, J = 7.2 Hz, IH), 7.47 (dd, J = 2.0, 7.2Hz, IH), 7.33 (m, IH), 7.27 (m, IH), 7.08 (s, 3H), 6.90 (d, J = 1.6 Hz, IH), 6.74-6.72 (m, IH), 4.87-4.84 (m, IH), 4.19 (s, 4H), 2.48-2.42 (m, 18H), 1.27 (d, J= 4.0 Hz, 6H).
Example 93
Synthesis of Ru complex 11c
The synthetic procedure is the same as in Example 85. 733 mg of yellow-green solid product 11c was obtained (yield: 95%).
Ru complex (11c) 1HNMR (400 MHz, CDC13): δ 16.56 (s, 1H), 7.47 (dd, J = 2.0, 7.2 Hz, 1H), 7.31-7.27 (m, 5H), 7.20-7.19 (m, 3H), 7.08-6.94 (m, 1H),6.72 (d, J = 6.4Hz, 1H), 4.85-4.81 (m, 1H), 4.18 (s, 3H), 3.85 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J= 6.0 Hz, 6H).
Example 94
Synthesis of Ru complex lid
The synthetic procedure is the same as in Example 85. 403 mg of yellow-green solid product lid was obtained (yield: 52%).
Ru complex (lid) 1HNMR (400 MHz, CDC13): δ 16.49 (s, 1H), 8.67 (m, 2H), 7.47 (d, J= 5.6 Hz, 1H), 7.37 (m, 3H), 7.08 (s, 3H),6.73 (d, J= 6.8Hz, 1H), 4.85-4.83 (m, 1H), 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J= 4.4 Hz, 6H). Example 95
Synthesis of Ru complex lie
The synthetic procedure is the same as in Example 85. 458 mg of yellow-green solid product lie was obtained (yield: 59%).
It is confirmed by Ru complex (lie) 1HNMR (400 MHz, CDC13): δ 16.52 (s, 1H), 8.60-8.51 (m, 2H), 7.67 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 2.4 Hz, 1H), 7.06 (s, 4H), 6.88 (d, J = 2.4 Hz, 1H), 6.71 (d, J = 8.0 Hz, 2H), 4.84-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 18H), 1.24 (d, J= 4.0 Hz, 6H).
Example 96
Synthesis of Ru complex llf The synthetic procedure is the same as in Example 85. 733 mg of yellow-green solid product llf was obtained (yield: 97%).
Ru complex (llf) 1HNMR (400 MHz, CDC13): δ 16.57 (s, 1H), 7.63-6.69 (m, 11H), 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24 (d, J = 4.0 Hz, 6H).
Example 97
Synthesis of Ru complex llg
The synthetic procedure is the same as in Example 85. 330 mg of yellow-green solid product llg was obtained (yield: 37%).
Ru complex (llg) 1HNMR (400 MHz, CDC13): δ 18.67 (s, 1H), 8.40 (m, 1H),
7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), 2.63-2.27 (m, 19H), 1.00 (d, J = 4.0 Hz, 6H).
Example 98
Synthesis of Ru complex llh
The synthetic procedure is the same as in Example 85. 619 mg of yellow-green solid product llh was obtained (yield: 73 %).
Ru complex (llh) 1HNMR (400 MHz, CDC13): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), 7.19-6.93 (m, 10H), 6.60 (d, J = 7.6 Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m, 6H).
Example 99
Synthesis of Ru complex llj
The synthetic procedure is the same as in Example 85. 416 mg of yellow-green solid product llj was obtained (yield: 49%).
Ru complex (llj) 1HNMR (400 MHz, CDC13): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), 2.62-2.17 (m, 19H), 1.00 (d, J = 4.0 Hz, 6H).
Example 100 Synthesis of Ru complex Ilk
The synthetic procedure is the same as in Example 85. 561 mg of yellow-green solid product Ilk was obtained (yield: 63%).
Ru complex (Ilk) 1HNMR (400 MHz, CDC13): 518.69 (s, 1H), 8.42 (s, 2H), 7.62-6.93 (m, 16H), 6.60 (dd, J = 2.0, 7.6 Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d, J= 4.4 Hz, 6H).
Example 101
Synthesis of Ru complex 11m
The synthetic procedure is the same as in Example 85. 685 mg of yellow-green solid product 11m was obtained (yield: 78%).
Ru complex (11m): 1H- MR (400 MHz, CDC13): δ 16.85 (s, 1H), 8.42-7.07 (m, 15H), 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29 (d, J= 4.4 Hz, 6H).
Example 102
Synthesis of Ru complex lln
The synthetic procedure is the same as in Example 85. 704 mg of yellow-green solid product lln was obtained (yield: 85%).
Ru complex (lln) 1HNMR (400 MHz, CDC13): 516.85 (s, 1H), 8.47-6.85 (m, 16H), 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29 (d, J= 4.4 Hz, 6H).
Example 103
Synthesis of Ru complex lip
The synthetic procedure is the same as in Example 85. 797 mg of yellow-green solid product lip was obtained (yield: 96%).
Ru complex (lip) 1HNMR (400 MHz, CDC13): 517.00 (s, 1H), 8.47-6.82 (m, 11H), 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J= 4.4 Hz, 6H).
Example
Synthesis of Ru complex llq The synthetic procedure is the same as in Example 85. 365 mg of yellow-green solid product llq was obtained (yield: 47%).
Ru complex (llq) 1HNMR (400 MHz, CDC13): δ 17.33 (s, 1H), 8.71 (s, 1H), 8.56 (d, J = 3.2 Hz, 1H), 7.84 (d, J = 6.0Hz, 1H), 7.41-7.34 (m, 1H), 7.23-7.21 (m, 1H), 7.01 (dd, J= 3.2, 9.6 Hz), 5.23-5.21 (m, 1H), 2.37-0.90 (m, 33H).
Example 105
Synthesis of Ru complex 11 r
The synthetic procedure is the same as in Example 85. 604 mg of yellow-green solid product llr was obtained (yield: 69%).
Ru complex (llr) 1HNMR (400 MHz, CDC13): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.50-6.39 (m, 20H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).
Example 106
Synthesis of Ru complex 4i
Starting material 4-SM (44g, lOOmmol) and anhydrous ethanol (250mL) were added into a 500 mL three-necked flask filled with inert gas (Ar), followed by adding NaOEt (400mmol, 4.0eq) was quickly added with agitation. The reaction mixture was heated to 60 °C . After the reaction was completed in 0.5-1.0 hr, 120 mL of water was added into flask, and the aqueous layer was extracted with pentane (200 mL><3), and the combined organic layers were washed with brine (150 mL><2) solution, then dried over NaS04 and concentrated to obtain about 50 mL of crude carbine intermediate 4-1 directly for next step at 0-5 °C .
RuCl2(PPh3)3 (29g, 30mmol) was dissolved in 250 mL of anhydrous DCM in a 500 mL three-neck flask filled with inert gas (Ar), and the DCM solution was cooled to -70 °C, then the previously prepared crude carbine intermediate 4-1 (50 mL) was added into the DCM solution at -70 °C . After 10 min, the solution was heated to room temperature, and CuCl (lOOmmol) was added. After completed in 30 min, the reaction solution was filtered and purified by silica gel column chromatography (eluting solution: n-hexane:DCM = 2: 1 to pure DCM). The product was concentrated and washed by anhydrous n-hexane. After dried by vacuum, the Ru complex intermediate 4-2 (19.3g) was obtained.
The intermediate 4-2 (lO.Ommol) and tricyclohexylphosphine (PCy3, 20mmol, 2.0eq.) were dissolved in DCM (30mL) in a 250 mL three-neck flask filled with inert gas (Ar), then stirred at 20 °C for about 30 min. After completed, the crude product was purified by flash column to obtain dark-green solid. The solid product was washed with anhydrous methanol and n-hexane to obtain green solid product 4i (crude yield: 60-70%). The product 4i is not stable and difficult to analyze the structure by 1HNMR. But the crud Ru complex 4i can be used directly to prepare 4j in next step.
Example 107
Synthesis of Ru complex 4j
The Ru complex 4i (5.0mmol) and a ligand H2IMes(H)(CCl3) (4-4, lO.Ommol,
2.0eq.) were dissolved in anhydrous toluene (30mL) in a 100 mL two-necked flask filled with Ar gas. The reaction mixture was heated to 80 °C for 1.5hr. After the reaction was completed, the solution was cooled and filtered, then purified by flash column to obtain dark-green product. The crude product was washed by methanol and pentane-DCM to offer 2.3g of stable green solid product 4j (yield: 59%).
Ru complex 4j is confirmed by 1HNMR (400 MHz, CDC13): δ 18.88 (s, lH, Ru=CH), 7.57-6.44 (m, 11H, aromatic H), 5.36 (t, J= 13.2 Hz, 1H, H), 4.16-4.02 (m,
5H, NCH2, NCH2CH2N), 4.01 (d, J = 13.2 Hz, 1H, NCH2), 2.75-2.00 (m, 19H,
CH(CH3)2, aromatic CH3), 1.01-0.90 (m, 6H, CH(CH3)2).
Example 108
Synthesis of Ru complex llh
The Ru complex 4j (0.2mmol) and 4-chlorin pyridine 4-chlorin pyridine ligand (4-5, 2.0mmol) were reacted directly to form another Ru complex llh in 10 mL of anhydrous DCM in a 100 mL three-neck flask filled with inert gas (Ar). Preparation method and result of the Ru complex llh was the same as described in Example 92. 619 mg of yellow-green solid product llh was obtained (yield: 73%). Ru complex llh is confirmed by 1HNMR (400 MHz, CDC13): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), 7.19-6.93 (m, 10H), 6.60 (d, J= 7.6 Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m, 6H).
Example 109
Synthesis of Ru complex 2j
SM-2b (10.4g, 50 mmol) and RuCl2(PPh3)3 (48g, 50 mmol) were dissolved in 250 mL of anhydrous THF in a 500mL three-neck round-bottom flask filled with inert gas (Ar) and reacted to form the Ru complex 2h. The reaction mixture was stirred at room temperature until completed (monitored by TLC), and the reaction product 2h was worked out by precipitation in hexane and dried over 42g (yield: 95%).
2h (8.9g, 10 mmol) and a new ligand 3x (3.1 g, 11 mmol) with CuCl (12 mmol) were dissolved in 100 mL of anhydrous DCM in a 500mL three-neck round-bottom flask filled with inert gas (Ar) and reacted to form another Ru complex 2j. The reaction mixture was stirred until complete (monitored by TLC), and the reaction product 2j was worked out and dried over (6.2g, yield: 89%). The product 2j is not very stable and directly used for next step to prepare new developed Ru complexes Ila and lib.
Example 110
Synthesis of Ru complex 4x
2j (0.71g, 1.0 mmol) and a phosphine ligand PCy3 (4-3, 1.5 mmol) were dissolved in 10 mL of anhydrous DCM in a 50mL three-neck flask filled with inert gas (Ar) and reacted to form the Ru complex 4x. The reaction mixture was stirred until completed (monitored by TLC), the reaction product was precipitated in MeOH and filtered and purified by flask column. 0.56g of green solid product 4x was obtained, yield: 78%.
The Ru complex 4x prepared in this Example 110 is confirmed by 1HNMR as the same as in Example 21. Example 111
Synthesis of Ru complex 4aa
Ru complex 4x (0.72g, 1.0 mmol) and heterocyclic ligand H2IMes(H)(CCl3) (4-4, 48g, 50 mmol) were dissolved in 10 mL of anhydrous Toluene in a 50mL three-neck flask filled with inert gas (Ar) and reacted to form the Ru complex 4x. The reaction mixture was stirred until complete (monitored by TLC), the reaction solution was filtered and purified by flask column. 0.55g of green solid product 4x was obtained (yield: 73%).
The Ru complex 4aa prepared in this Example 111 is confirmed by 1HNMR as the same as in Example 24.
Example 112
RCM reaction
RCM test by selecting the Ru Complexes of Examples 1-108 as Catalyst
General Procedure for RCM Catalyzed by Ru Complex in DCM: Olefin substrate (15 or 17, 50mg/each, respectivrly) was dissolved in 1.0 mL of freshly distilled DCM in a 15mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (2 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The kinetic data for conversion of RCM reactions in Equations 1-2 were determined by HPLC at 10 min., 30 min. 1.5 hr, 3.0 hr and until completed overnight. The RCM product (16 and 18, respectivrly) was determined and the conversion results of RCM reactions were listed in Tables 1-1, 1-2, 1-3, 1-4, 1-5, and 2 above, respectively.
The RCM product 16 is confirmed by 1HNMR (400 MHz, CDC13): δ 7.72 (d, J = 8.2 Hz„ 1H), 7.32 (d, J = 8.0 Hz, 1H), 5.66 (d, J = 4.4 Hz, 1H), 4.11 (d, J = 4.4 Hz, 1H), 2.42 (s, 3H). in z calculated: 222.1; found: 222.2.
The RCM product 18 is confirmed by 1HNMR (400 MHz, CDC13): δ 7.78 (d, 2H, J = 8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). (M+H+) : m/z calculated : 300.1 , found : 300.2. Example 113
Catalyst Screening for Cross Metathesis Reaction
CM test by selecting Ru Complexes of Examples 1-108 as Catalyst(s)
General Procedure for CM Catalyzed by Ru Complex in DCM: Olefin substrate (19, 200mg/each, respectivrly) was dissolved in 3.0 mL of freshly distilled DCM in a 15mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The CM reaction results are described in section of Equation 3 above. Example 114
Catalyst Screening for ROMP reaction without solvent
ROMP test by selecting Ru Complexes of Examples 1-108 as Catalyst(s)
General Procedure for ROMP Catalyzed by Ru Complex without solvent for some liquid olefin substrates: Olefin substrate (21, 23 or 25, 5mL/each, respectivrly) was added into a 25mL flat-bottom bottle under Ar at 40-50°C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added with agitation. The kinetic data and ROMP results for products 22, 24 and 26 are described in each section of Equation 4-6 above, respectively. Example 115
Catalyst Screening for ROMP reaction with solvent
ROMP test by selecting Ru Complexes of Examples 1-108 as Catalyst(s)
General Procedure for ROMP Catalyzed by Ru Complex in solution: 0.5g of cyclo-olefin substrate (21, 23, 25, 27, 29, or 31, respectivrly) was dissolved in 10 mL of freshly distilled DCM in a 25mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The ROMP results for products 22, 24, 26 , 28, 30 and 32 are described in each section of Equation 4-9 above, respectively. Example 116
Catalyst Screening for Depolymerization of nitrile butadiene rubber by Metathesis
Metathesis Depolymerization test by selecting Ru Complexes from Examples 1-108 as Catalyst(s)
General Procedure for depolymerization Catalyzed by Ru Complex: 60g of nitrile butadiene rubber ( BR) was dissolved in 500 mL of anhydrous chlorobenzene in a 1.0L well-sealed steel reactor under Ar at 30 °C, then the Ru catalyst (4ab, 0.04 wt%, one of Ru complexes selected from Examples 1-108) was added into chlorobenzene solution. The depolymerization by Ru catalyst was conducted overnight to produce lower molecular weight rubber as shown in Equation 10. The depolymerized butyl rubber product was precipitated in MeOH, and dried over 97% of yield. The final rubber product has a Mw of 2.78E+05, a Mn of 1.586E+5, and a Mooney viscosity of 60.3.Example 117
Catalyst Screening for Metathesis and Hydrogenation reactions of nitrile butadiene rubber
Metathesis and Hydrogenation test by selecting Ru Complexes from Examples 1-108 as Catalyst(s)
General Procedure for Metathesis and Hydrogenation Catalyzed by Ru Complex in solution: 60g of nitrile butadiene rubber (NBR, Raw Material) substrate was dissolved in 500 mL of anhydrous chlorobenzene in a l .OL steel well-sealed reactor under Ar, then Ru catalyst (4aa, 0.07 wt% of Ru complex selected from Examples 1-108, respectively) was added into chlorobenzene solution, followed by adding hydrogen under high pressure 5MPa, and finally heated upto 130°C overnight. The hydrogenated nitrile butadiene rubber product (HNBR) by Ru catalyst was prepared with lower molecular weight and higher hydrognation degree as shown in Equation 11. The depolymerized and hydrogenated butyl rubber product was precipitated in MeOH, and dried over 98% of yield. The final product has a Mw of 1.60E+05, a Mn of 1.12E+05, an Iodine value of 12.6, and a hydrogenation degree of greater than 95%.
Example 118 Catalyst Screening for Hydrogenation and Metathesis reactions of nitrile butadiene rubber
Metathesis and Hydrogenation test by selecting selecting Ru Complexes from Examples 1-108 as Catalyst(s)
General Procedure for Metathesis and Hydrogenation Catalyzed by Ru Complex in solution: 60g of nitrile butadiene rubber (NBR) substrate was dissolved in 500 mL of anhydrous chlorobenzene in a 1.0L steel well-sealed reactor under Ar, then hydrogen was added under high pressure 5MPa, followed by adding Ru catalyst (4aa, 0.1 wt% of Ru complex selected from Examples 1-108) into chlorobenzene solution, then heated upto 130°C overnight. The hydrogenated nitrile butadiene rubber product (HNBR) by Ru catalyst was prepared with higher hydrognation degree and lower molecular weight as shown in Equation 12. The hydrogenated butyl rubber product was precipitated in MeOH, and dried over 98% of yield. The final product has a Mw of 1.80E+05, a Mn of 1.07E+05, an Iodine value of 3.1, and a hydrogenation degree of greater than 99%.

Claims

What is claimed is:
1. A ligand of metal complex having the following structure la or lb
Figure imgf000111_0001
la lb
Wherein:
Z is CH2= or Ts HN=
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, Ci-C20 alkyl, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C2o heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— X" is either single bond or double bond;
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C20 alkyl, C6-C20 aryl, C6-C20 aryloxy, C2-C20 heterocyclic aryl, Ci-C20 alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
R1 is H, Ci-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C6-C20 arylenyl, Ci-C20 alkoxy, Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group;
R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C2o arylaminocarbonyl, Ci-C2o alkylamido, C6-C2o arylamido, Ci-C2o alkylaminosulfonyl, C6-C2o arylamino sulfonyl, Ci-C2o sulfonylamido, C3-C2o heteroaryl or C2-C2o heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
2. The ligand of metal complex according to claim 1, wherein the structure Ia-Ib,
Z is CH2= or TsNHN=;
m = 0 or 1, n = 0 or 1 ;
When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, C1-C15 alkyl, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-Cis heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group;
R1 is H, C1-C15 alkyl, C2-Ci5 alkenyl, C6-C15 aryl, C6-C15 arylenyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C15 arylthio, C6-C15 aryloxy, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group;
R2 is H, C1-C15 alkyl, C6-C15 aryl, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 aminocarbonyl, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Ci5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-C15 aryl, C6-C15 aryloxy, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-C15 arylaminocarbonyl, C1-C15 alkylamido, C6-C15 arylamido, C1-C15 alkylaminosulfonyl, C6-C15 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Ci5 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
3. The ligand of metal complex according to claim 2, wherein the structure Ia-Ib,
Z is CH2= or Ts HN=;
m = 0 or 1, n = 0 or 1 ;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-C8 aryloxy, Ci-C8 alkoxycarbonyl, C6-C8 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-Ci2 heterocyclic amino group;
When m = 1, X is nitrogen, oxygen, sulfur, CH, CH2, carbonyl; Y is oxygen, nitrogen, CH, CH2, imino, H, C1-C15 alkyl, Ci-C8 alkoxy, C6-Ci5 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH,
CH2, Ci-C8 alkyl, C6-C8 aryl, C6-C8 aryloxy, C2-C8 heterocyclic aryl, Ci-C8 alkylamino, C6-C8 arylamino or C2-C8 heterocyclic amino group;
R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl;
R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl;
1 2 3 4 5 6 7
E, E , E , EJ, E , E E° and E' are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
4. The ligand of metal complex according to claim 3, wherein the structure Ia-Ib, Z is CH2= or TsNHN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH2, H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group;
When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond;
When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl;
R1 is H;
when n = 1, R2 is methyl, ethyl, or isopropyl; when n = 0, R2 is H, halogen,
C1-C4 alkyl or C1-C4 alkoxy in structure la.
E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl;
E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
E3 is H;
E4 is H or C1-C4 alkyl;
E5 and E6 is H, halogen, C1-C4 alkyl or Ci-C6 alkoxy;
E7 is H or C1-C4 alkyl.
5. A transition metal com lex having the following structure Ila or lib,
Figure imgf000114_0001
Ila lib
wherein: m = 0 or 1, n = 0 or 1;
When n = 0; p = 0 or 1; when n = 1, p = 0;
M is a transition metal;
L1 and L2 are the same or different and each selected from halogen anion (CI", Br" or I"), RC(0)0" or ArO" anion;
L is an electron-donating ligand;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— x" is either single bond or double bond;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
When n = 0 and p = 1, L3 is an electron-donating ligand;
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C2o alkyl, C6-C2o aryl, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group;
R1 is H, Ci-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C6-C20 arylenyl, Ci-C20 alkoxy, Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group;
R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, Ci-C2o alkoxy, Ci-C2o alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, arylox halogen atom or heterocyclic group.
6. The transition metal complex according to claim 5, wherein L is heterocyclic carbene ligand or phosphine P(R8)2( 9) having the following structure Ilia, Illb, IIlc, or Hid:
Figure imgf000116_0001
Ilia Illb IIlc Hid
Wherein, q = 1, 2 or 3;
R4 and R5 are each C1-C20 alkyl, C6-C20 aryl, C1-C20 alkylamido, C6-C20 arylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R6 and R7 are each H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C2-C20 heterocyclic, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R8 and R9 are each C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl or C2-C20 heterocyclic group.
7. The transition metal complex according to claim 6, wherein L is formula Ilia or Hid; and in Ilia, q = 1 or 2, R4 and R5 each is aryl, R6 and R7 each is H.
8. The transition metal complex according to claim 6, wherein L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy).
9. The transition metal complex according to claim 5, wherein the structure Ila or lib: M is ruthenium ( u), wolfram (W) or nickel (Ni);
m = 0 or 1, n = 0 or 1;
L1 and L2 each is chloride (Cf);
L is Ilia or Hid; wherein q, R4, R5, R6, R7, R8 and R9 each is as defined in claim 6; R1, R2, E, E1, E2, E3, E4, E5, E6 and E7 each is as defined in claim 2.
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-C15 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 0, p = 0 or 1; when n = 1, p = 0.
When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Cis alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylamino sulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Cis heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group;
10. The transition metal complex according to claim 9, wherein the structure Ila or lib,
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-Ci2 aryloxy, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C8 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 0, p = 0 or 1 ; when n = 1, p = 0.
When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-Ci2 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylamino sulfonyl, Ci-C8 sulfonylamido, C3-Ci2 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group;
When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C8 alkyl, C6-Ci2 aryl, C6-Ci2 aryloxy, C2-Ci2 heterocyclic aryl, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group;
R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl;
R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl;
E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
11. The transition metal complex according to claim 10, wherein the structure Ila or lib:
M is ruthenium;
L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy).
L1 and L2 each is chloride anion;
m = 0 or 1, and n = 0 or 1;
When m = 0, Y is CH2, H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group;
When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond;
When n = 0, p = 0 or 1; when n = 1, p = 0;
When n = 0 and p = 1 , L3 is one substituted pyridine at the meta-position or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to ruthenium cation, wherein the substituents at the meta-position or para-position of pyridine are each selected from halogen, nitro, C1-C3 alkyl, C1-C3 alkoxy, Ci-C6 alkylamino, unsubstituted or substituted C6-Ci2 aryl;
When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl;
R1 is H;
when n = 1, R2 is methyl, ethyl, or isopropyl; when n = 0, R2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure Ila.
E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl; E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
E3 is H;
E4 is H or C1-C4 alkyl;
E5 and E6 is H, halogen, C1-C4 alkyl or C1-C5 alkoxy;
E7 is H or C1-C4 alkyl.
12. A method of carrying out a metathesis reaction with olefin substrate, comprising intramolecular ring-closing metathesis (RCM), intermolecular cross metathesis (CM), acyclic diene metathesis (ADMET) or ring-opening metathesis polymerization (ROMP) of cyclo-olefin substrate in the presence of one or more catalysts of claim 5.
13. The method according to claim 12, wherein cyclo-olefin substrate for ROMP is selected from dicyclopentadiene (DCPD), norbornene, cyclooctene, or a kind of tensional cycloolefin; each is optionally substituted or unsubstituted with one or more of F, CI, Br, C1-C15 alkyl, Ci-C 15 alkoxy, C1-C15 alkylthio, C2-Ci5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylaminosulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Cis heterocyclic group.
14. A cycloolefin substrate having the following structure Via- Vic;
Figure imgf000120_0001
Via VIb Vic
Wherein, r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, or C1-C15 heterocyclic amido group; G is a group of compounds with specific properties and uses; each is optionally selected from commercial drugs or liquid crystal monomers;
R10 and R11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C1-C15 alkylcarbonyl, C1-C15 alkyloxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C1-C15 alkylsulfonyl, C1-C15 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, Ci-C 15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
15. The cycloolefin substrate according to claim 14, wherein r =1, 2, 3 or 4; s = 1, 2, 3 or 4;:
A is O, S, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 aryloxy, C1-C15 alkylthio, Ci-C8 alkoxycarbonyl, Ci-C8 alkylamino, C6-Ci2 arylamino, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, or Ci-C8 heterocyclic amido group;
G is a kind of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs;
R10 and R11 are each H, halogen, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, C2-Q heterocyclic, C3-C12 heterocyclic aryl, Ci-C8 alkylcarbonyl, Ci-C8 alkyloxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, Ci-C8 alkylsulfonyl, Ci-C8 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-Cg alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heteroaryl or C2-C8 heterocyclic group.
16. The cycloolefin substrate according to claim 15, wherein in structure Via- Vic, r = 1 or 2, and s = 1 or 2;
A is O, CH2, C1-C5 alkyl-amino, C1-C5 alkoxy, C1-C5 alkylaminocarbonyl or C1-C5 heterocyclic amido group;
"Linker" is Ci-C6 alkyl, C1-C5 alkoxy, C1-C5 alkylthio, C1-C5 alkoxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido or C6-Ci2 arylamido group;
R10 and R11 are each H, C1-C5 alkoxy, C6-Ci2 aryloxy, C1-C5 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido, C6-Ci2 arylamido, liquid crystal monomer or modified prodrugs.
17. The cycloolefin substrate according to claim 15, wherein G is a kind of optionally modified prodrug of commercial drug Lipitor having the following structure Vlla-VIId:
Figure imgf000122_0001
Vila Vllb VIIc Vlld
Wherein R12 is cyclopropyl, C1-C15 alkly, C3-C15 cycloalkyl, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15
alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heterocyclic aryl or C2-C15 heterocyclic group.
18. The cycloolefin substrate according to claim 17, wherein R12 is cyclopropyl, Ci-C6 alkly, C3-C6 cycloalkyl, Ci-C6 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C6 alkylamino, C6-Ci2 arylamino, Ci-C6 alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heterocyclic aryl or C2-C6 heterocyclic group.
19. A method of making a quality-modified polymer having the following structure Villa or Vlllb in the resence of one or more mixed catalysts of claim 5.
Figure imgf000123_0001
Villa Vlllb (PDCPD)
20. A functional polymer, comprising a modified prodrug or functional group G having the following structure IXa-IXc:
Figure imgf000123_0002
IXa IXb
Wherein: r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, or C1-C15 heterocyclic amido group;
G is a group of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomer or modified prodrugs;
R10 and R11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C1-C15 alkylcarbonyl, C1-C15 alkyloxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C1-C15 alkylsulfonyl, C1-C15 alkylsulfonamido, liquid crystal monomer or modified prodrug; "Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
21. The functional polymer according to claim 20, wherein r, s, A, "Linker", R10 and R11 each is as defined in claim 16;
Wherein G is a kind of optionally modified pro-drug of Lipitor having the following structure VHa-VIId:
Figure imgf000124_0001
Vila Vllb VIIc Vlld
Wherein: R12 is as defined in claim 18.
22. A method of making a modified nitrile butadiene rubber (NBR) or styrene-butadiene rubber (SBR) by depolymerization in the presence of one or more mixed catalysts of claim 5 at 30-100°C.
23. A method of making a depolymerized HNBR (hydrogenated nitrile butadiene rubber) or styrene-butadiene rubber (SBR) by adding one or more mixed catalysts of claim 5 first to carry out depolymerization of NBR, followed by adding hydrogen into the reaction under high pressure for hydrogenation at 60-150°C.
24. A method of making a hydrogenated nitrile butadiene rubber (HNBR) or styrene-butadiene rubber by adding hydrogen under high pressure first, followed by adding one or more mixed catalysts of claim 5 at 60-150°C.
25. A use of catalysts of claim 5 in depolymerization of a rubber comprising at least one carbon-carbon double bond.
26. A use of catalysts of claim 5 in hydrogenation of a rubber comprising at least one carbon-carbon double bond.
27. A process of making a modified polymer Villa- VHIb, functional polymer IXa-Ixb in the presence of one or more mixed catalysts of claim 5.
28. A method of making functional polymers, comprising reacting one or more monomers in the presence of one or more mixed catalysts of claim 5.
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