CN114174312A - 空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催化剂的用途 - Google Patents

空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催化剂的用途 Download PDF

Info

Publication number
CN114174312A
CN114174312A CN202080053726.5A CN202080053726A CN114174312A CN 114174312 A CN114174312 A CN 114174312A CN 202080053726 A CN202080053726 A CN 202080053726A CN 114174312 A CN114174312 A CN 114174312A
Authority
CN
China
Prior art keywords
alkyl
formula
different
same
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080053726.5A
Other languages
English (en)
Inventor
J·科尔奈拉
L·纳特曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP19189236.3A external-priority patent/EP3771707A1/en
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of CN114174312A publication Critical patent/CN114174312A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure
    • C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
    • C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems 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 carbon atoms of the nitrogen-containing ring
    • C07D217/24—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/348—1,4-additions, e.g. conjugate additions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B01J2231/4216—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with R= alkyl
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4238—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R'
    • B01J2231/4244—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R' with R= alkyl
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4238—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R'
    • B01J2231/425—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R' with R'= alkyl
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • 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
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及空气稳定的、二元Ni(0)‑烯烃络合物及其在有机合成中的用途。

Description

空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催 化剂的用途
本发明涉及一种空气稳定的二元Ni(0)-烯烃络合物和它们用于有机合成的用途。
近年来，镍(Ni)催化已经变成一个日益增长和强大的研究领域，这归因于对于有机合成的新的分支和反应性模式。在这些努力中，Ni(0)-烯烃络合物已经变成了一个有效的Ni(0)源，这归因于它们对于配体交换的高亲和性。例如Ni(COD)2(双(环辛二烯)Ni(0))已经变成了用于开发新的催化反应性的基础Ni(0)源。
但是，仅仅带有烯烃作为配体的二元Ni(0)络合物当曝露于空气时遭受了大的不稳定性和快速分解的问题，这因此将它的操作限制到Schlenk技术或者处于惰性气氛下的手套箱。
在1960年代，DE 1191375 AS公开了作为烯烃和Ni盐的反应，合成第一个二元金属-烯烃络合物。从这个公开文献之后，Ni(0)-烯烃化合物，特别是Ni(COD)2已经充当了预催化剂来展示多个转变，其影响了化学科学的各个方面。此外，Ni(COD)2和全反式-Ni(CDT)已经充当了用于不同的在数吨规模发生的重要工业方法的催化剂，即，烯烃化合物的聚合和环三聚。
但是，在均相催化的情况中，Ni(COD)2已经变成了用于反应发现的主要的(如果不是唯一的)Ni(0)源(图1a)。确实地，Ni(COD)2是市售的，这归因于它在低温在惰性气氛下显著的稳定性。Ni(COD)2中的烯烃配体当与具有更大亲核性的对应物例如膦、二胺或者碳烯竞争时的不安定性已经将这种化合物置于反应发现的前沿，因此在多种催化转化中明显具有优势。
但是，虽然它具有重要的性能，但是使用Ni(COD)2是与它的高的不稳定性相关联的，并且在曝露于空气时立即分解，这导致了冗长的操控，并且需要使用手套箱或者Schlenk技术。可选择的二元Ni(0)-烯烃络合物局限于Ni(CDT)(顺式或者反式)、Ni(COT)2或者Ni(C2H4)3，其甚至更不稳定的和极端空气敏感(图1a)。
由于这些原因，化学家们多年来孜孜以求地研究可选择的Ni(0)前体，其在空气下是稳定的，因此认识到这样的预催化剂从制备时间和反应设施的观点，将允许开发易行的和高度实际的方法。
确实地，Ni(0)-烯烃络合物的独特性能和反应性仍然是最重要的，并且化学家已经付出了巨大的努力来在需氧条件下操控这样的化合物，如开发其它的Ni(II)预催化剂(图1b)或者石蜡胶囊(paraffin capsule)(其允许在台式设施中使用Ni(COD)2)所示例的。
但是，仍然需要为使用空气稳定的Ni(0)前体提供实际的解决方案。
本发明人已经开发了一组独特的如由Ni(Xstb)3图示的16-电子二元Ni(0)-茋络合物的合成，并研究了它们的催化活性，其中X描述了不同的取代样式。
与全部所报道的16-和18-电子Ni(0)-烯烃络合物相反，Ni(Xstb)3当在-18℃的冰箱中存储时，在空气下稳定数月，同时没有明显的分解。所述络合物可以不使用手套箱或者Schlenk来操控，并且是高度模块化的，因此允许与Ni催化中的许多常用的配体例如二胺、膦、N-杂环碳烯(NHC)等进行配体交换，从而提供了明确限定的Ni(0)-L物质。此外，它们的催化活性是以Ni(COD)2为基准的，并且显示出是用于多种多样的不同的Ni催化的反应的优异前体。
本发明因此涉及Ni(R)3-络合物，其中Ni表示Ni(0)和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure BDA0003487304920000031
其中R1-R10可以是相同或者不同的，和选自H、Cl、Br、F、CN、C1-C8烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，
其中R11-R12可以是相同或者不同的，和选自H、C1-C8烷基、C3-C6环烷基、-O-C1-C8烷基或者-O-C3-C6环烷基，
条件是R1-R12中的至少一个不是氢。
在本发明上下文所示的本发明的Ni(R)3-络合物中，Ni表示Ni(0)。
在本发明的Ni(R)3-络合物的另一实施方案中，R是相同或者不同的，并且在式(I)中，R1-R5中的至少一个和R6-R10中的至少一个是相同或者不同的，和选自Cl，Br，F，CN，C1-C8烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，优选选自C1-C8烷基，其可以非必要地是支化的和/或用一个或多个卤素取代，和其它的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H，C1-C8烷基，C3-C6环烷基，-O-C1-C8烷基或者-O-C3-C6环烷基。
在本发明的Ni(R)3-络合物的仍然另一实施方案中，R是相同或者不同的，并且在式(I)中，R3和R8是相同或者不同的，和选自C1-C8烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，和其它的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H，C1-C8烷基，C3-C6环烷基，-O-C1-C8烷基或者-O-C3-C6环烷基。
在本发明的Ni(R)3-络合物的另一实施方案中，R是相同或者不同的，并且在式(I)中，R3和R8是相同或者不同的，和选自支化的C3-C8烷基例如异丙基，叔丁基，新戊基，其可以非必要地用一个或多个卤素取代，和其它的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H，C1-C8烷基，C3-C6环烷基，-O-C1-C8烷基或者-O-C3-C6环烷基。
在本发明的Ni(R)3-络合物的仍然另一实施方案中，R是相同的，并且在式(I)中，R3和R8是相同或者不同的，和选自C1-C8全氟烷基，和其它的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H，C1-C8烷基，C3-C6环烷基，-O-C1-C8烷基或者-O-C3-C6环烷基。
在本发明的Ni(R)3-络合物的仍然另一实施方案中，R是相同的，并且在式(I)中，R3和R8每个是C1-C8全氟烷基，优选CF3，和其它的R1-R10和R11-R12是氢。
在本发明中，烷基目的是表示具有1-8个碳原子的任何烷基，包括支化的烷基，例如甲基，乙基，丙基，异丙基，丁基，异丁基，叔丁基，戊基，新戊基，异戊基，己基，异己基，庚基，异庚基，辛基，异辛基。
在本发明中，环烷基目的是表示具有3-6个碳原子的任何环烷基，包括烷基例如环丙基，环丁基，环戊基，环己基和取代的烷基环。
每个烷基或者环烷基可以用一个或多个卤素取代，特别是氟。
本发明还涉及一种制备本发明的空气稳定的Ni(R)3-络合物的方法，其中Ni表示Ni(0)和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure BDA0003487304920000041
其中R1-R10可以是相同或者不同的，和选自H，Cl，Br，F，CN，C1-C6烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，
其中R11-R12可以是相同或者不同的，和选自H，C1-C6烷基，C3-C6环烷基，-O-C1-C6烷基，或者-O-C3-C6环烷基，
其中选自NiF2、NiCl2、NiBr2、NiI2、Ni(OTf)2、Ni(BF4)2、Ni(OTs)2、Ni(甘醇二甲醚(glyme))Cl2、Ni(甘醇二甲醚)Br2、Ni(二甘醇二甲醚)Cl2、Ni(二甘醇二甲醚(diglyme))Br2、Ni(NO3)2、Ni(OR13)2(其中R13表示-C(O)-C1-C6-烷基，其是非必要地用一个或多个卤素取代的，优选用Cl或者F取代)、(乙酰基丙酮酸)2Ni、Ni(Ac)2或者其混合物的镍(II)化合物是在式Al(R14)3的烷基铝存在下，与式(I)的反式茋反应，优选与至少3当量，优选至少2当量的式(I)的反式茋反应，其中R14可以是相同或者不同的，和选自C1-C6烷基或者C3-C6环烷基。
在前述的本发明的制备空气稳定的Ni(R)3-络合物的一种实施方案中，式Al(R14)3的烷基铝选自Al(CH3)3或者Al(C2H5)3。
在前述的本发明的制备空气稳定的Ni(R)3-络合物的仍然另一实施方案中，R表示权利要求2-5任一项所定义的式(I)的反式茋。
在本发明方法的另一实施方案中，使用式(I)的反式茋，其中R1-R12中的至少一个不是氢。
在本发明的方法中，溶剂的选择不是关键的，只要溶剂是非质子非极性有机溶剂就行，其选自二乙醚，芳族溶剂例如苯，甲苯，具有5-8个碳原子的脂族烃溶剂例如戊烷，己烷或者其混合物。反应条件也不是关键的，并且该反应通常在-78℃到0℃，优选-30℃到-5℃的温度，在环境压力下和非必要地在惰性气氛下进行。该反应通常是用稍微化学计量过量的式(I)的反式茋(优选至少3当量)和式Al(R14)3的烷基铝(优选至少2当量)来进行，式(I)的反式茋和式Al(R14)3的烷基铝优选高达额外的10mol％。
本发明还涉及本发明空气稳定的Ni(R)3-络合物作为有机合成中的催化剂的用途，其中：
Ni表示Ni(0)，和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure BDA0003487304920000061
其中R1-R10可以是相同或者不同的，和选自H，Cl，Br，F，CN，C1-C6烷基，C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，和
R11-R12可以是相同或者不同的，和选自H，C1-C8烷基，C3-C6环烷基，-O-C1-C6烷基或者-O-C3-C6环烷基，
非必要地，条件是R1-R12中的至少一个不是氢。
催化性能
已经证实了与Ni催化中常用配体交换配体的能力，本发明人已经开始开发本发明的Ni(0)-烯烃络合物作为多个相关的有机转变中的Ni(0)源的催化性能。为此目的，本发明人以他们的催化剂在不同的Ni催化的转变中作为Ni(0)源为基准，并且将本发明Ni(0)-烯烃络合物的性能与Ni(COD)2和一些Ni(I I)预催化剂进行比较。所述催化性能是用催化剂(Ni(0)(4-CF3stb)3)和(Ni(0)(4-tBustb)3)来示例性开发的。
本发明人初始时开发了催化Suzuki偶合的可行性，这归因于它在现代合成中的极大重要性。使用本发明的Ni(0)-烯烃络合物作为预催化剂允许杂芳基硼酸和杂芳基溴化物以优异的产率来偶合(图4a.>99％)。
高度关注的另一反应是Ogoshi所报道的腈和二烯之间的氧化性环加成。虽然所述反应使用了较高的温度(130℃)，但是本发明的Ni(0)-烯烃络合物证实了稳定的和催化的能力，这提供了84％产率的产物(图4b)。
最近已经出现了基于Ni催化的C-H活化策略，其使用了Ni(0)作为预催化剂源。作为一个例子，Chatani证实了由简单的酰胺和炔烃来合成异喹啉酮(isoquinolone)。简单的PPh3据报道是用于这样的目的最佳配体；在这种情况中，本发明的Ni(0)-烯烃络合物还表现为是作为Ni(0)源的优异的候选者，其提供了优异的产率(图4c.94％)。
为了进一步测试本发明的Ni(0)-烯烃络合物作为催化剂的能力，本发明人将他们的关注点调节到形成重要的C-N键。为此目的，本发明人利用了用芳族胺和脂族胺二者来胺化芳基卤化物的报道。当使用SIPr作为配体时，本发明的Ni(0)-烯烃络合物平稳地提供了优异产率的产物(图4d.91％)。当使用芳族胺代替时，使用dppf作为配体，并且获得了向双芳族胺的平稳转化(图4e.90％产率)。值得指出的是在这个后者的例子中，一些Ni-络合物与所报道的相比需要稍微较高的温度，这大概归因于(dppf)Ni(0)(4-CF3stb)中间体的高稳定性(图3)，因此与它的Ni(COD)2类似物相比需要更高的能量来促进茋配体的离解。
将缩醛活化来用于芳基化最近由Doyle进行了报道。虽然存在着质子溶剂例如tAmOH，但是本发明的Ni(0)-烯烃络合物被证明是一种极好的候选者，其获得了优异的芳基化产率(图4f.85％)。低价Ni物质通过它的C-N键活化酰胺的能力已经被证实是一种用于有机合成的有力的断裂。本发明的Ni(0)-烯烃络合物在本文上下文中突出的特点在于由N-Me-Boc酰胺和色醇以高产率形成酯(图4g.65％)。本发明的Ni(0)-烯烃络合物还表现在是有力的烷基-烷基Negishi交叉偶合中优异的Ni(0)源，如图4h中所获得的58％产率的C-C键所示例。值得提及的是这最后两种反应是使用三联吡啶和PyBOX衍生物作为配体来成功进行的，因此凸显了本发明的Ni(0)-烯烃络合物容易转化为具有三齿配体的活性L-Ni(0)物质。
本发明的Ni(0)-烯烃络合物2所催化的芳基溴化物和乙烯基锌试剂之间的Negishi交叉偶合能够实现与所报告的相应的Ni(0)前体相比类似的产率(92％，图4i)。Ni(0)-烯烃络合物也已经作为前体用于产生非均相Ni(0)粒子，无需加入辅助配体。在本文上下文中，本发明的Ni(0)-烯烃络合物已经被证明是一种优异的候选者，如用硅烷还原硫甲基醚中所示(91％，图4j)。
最近，使用高度给电子的配体例如NHC与Ni(COD)2相组合已经成为经由C-H活化的加氢芳基化策略情形中的催化体系的选择。但是，已经注意到作为COD配体的加氢金属化的结果，这种催化剂和配体的具体组合导致形成了不期望的Niπ-烯丙基络合物。结构证据和反应性研究已经得出结论，即，这样的物质阻止了催化活性和周转率(turnover)。本发明人预期本发明的Ni(0)-烯烃络合物能够避免在某些C-H芳基化策略中所观察到的有害的路径，因此有利于生产性催化。为了测试这个假设，本发明人使用缺电子的芳烃检验了炔烃的直接加氢芳基化。如所报道的，将Ni(COD)2与IMes组合使用提供了痕量的加氢芳基化产物。另一方面，使用本发明的Ni(0)-烯烃络合物2在室温平稳反应，并且获得了显著的90％产率的产物(图5)。这个结果凸显了这样的事实，即，本发明的Ni(0)-烯烃络合物能够作为Ni(0)预催化剂，并且在一些情况中，当发生COD副反应时，它能够充当独特的候选者。重要地是要提到使用本发明的Ni(0)-烯烃络合物无需使用高度敏感的游离碳烯，和简单地使用母体HCl盐与碱的组合足以实现反应性。
重要地是要提到在其中本发明的Ni(0)-烯烃络合物是预催化剂的全部实施例中，反应设施是在开放空气环境中和在试验台(bench)进行的。因此，手套箱的使用是通过用于每个具体情况的最佳配体的敏感性来指示的，并且绝不通过Ni-烯烃预催化剂来指示。总之，这些结果凸显了Ni(Xstb)3(2-6)在多种催化情况中作为有效的Ni(0)源的竞争力。此外，当使用本发明Ni(0)-烯烃络合物时获得良好的产率凸显了它在打算使用不同的螯合性质或者亲核性的配体时的模块化性能。
本发明参考附图和实验部分来更详细地解释。
附图显示了：
图1.a：用于Ni催化的现有技术的二元Ni(0)烯烃络合物。
b：目前解决涉及Ni(0)物质的空气敏感性问题的策略；
c：以Ni(Fstb)3示例的本发明：一种空气稳定的16-电子Ni(0)-烯烃络合物
d：六个不同的本发明的Ni(Xstb)3络合物(1-6)，每个在每个芳基核上具有不同的芳基取代基(一个或多个)，以及它们的制备和稳定性。
图2合成络合物1和2：
反应条件：全反式-Ni(CDT)(1.0当量)，反式茋或者反式-(4-三氟甲基苯基)茋(分别是3.30和3.15当量)处于-5℃的THF或者Et2O中。
图3：络合物2在催化中与不同的常用配体的配体交换：
a)2(1.0当量)，dppf(1.0当量)，处于25℃的THF中，定量；
b)2(1.0当量)，bipy(1.0当量)，处于25℃的THF中，定量；
c)2(1.0当量)，PPh3(2.0当量)，处于25℃的THF中，定量；
d)2在-78℃的THF中的缓慢结晶。Ar＝p-CF3-C6H4。
图4：2在多个Ni催化的转变中的催化性能。
a.Suzuki交叉偶合；
b.环异构化反应；
c.C-H活化；
d.Buchwald-Hartwig C-N键形成，使用烷基胺；
e.Buchwald-Hartwig C-N键形成，使用芳基胺；
f.缩醛的C-O芳基化；
g.通过酰胺的C-N键活化形成酯；
h.烷基-烷基交叉偶合；
i.Negishi交叉偶合；
j.使用硅烷的C-SMe还原。
图5：络合物2避免了传统的COD副反应。
图6显示了催化剂6的两种工业上相关的转变和配位。
如图6A所示，还在两种工业上相关的转变中(其需要现有技术的Ni(COD)2)证实了与其它烯烃交换的配体的稳定性和便利性。如图6A所示，2M3BN(2-甲基-3-丁烯腈(44)-在Ni(4-tBustb)3(6)存在下Ni催化的异构化成3PN(3-戊烯腈，(45)，其在由丁二烯有效合成己二腈中是至关重要的，这种转变在纯净条件下借助于PPh3来进行，并且提供了接近于45(67％)的相当的反应性水平。另一方法是Ni催化的SHOP(Shell高级烯烃方法)(图6B)，其能够低聚乙烯来获得更高分子量的α-烯烃。在非最佳化条件下和没有预催化剂分离时，络合物6与图6B所示的配体混合物一起成功地高效催化了α-烯烃混合物的形成。这些结果凸显了6在工业相关设施中的潜力，因此为目前的Ni(0)催化剂提供了一种空气和温度稳定的替代选项。
虽然Ni(4-tBustb)3(6)可以被认为是空气稳定的Ni(COD)2的替代品，但是两种络合物的基础配位化学是明显不同的。例如，当Ni(COD)2与4.0当量的PPh3混合时，通常获得了Ni(PPh3)4和(PPh3)2Ni(COD)的不可分离的混合物(图6C，顶部)。另一方面，当使用6代替时，形成了向16-电子化合物45的完全转化(图6C，底部)。配位化学中的这些差异为现有的合成明确限定的L-Ni(0)-烯烃络合物的策略提供了正交工具(an orthogonal tool)。
通用实验备注
除非另有规定，否则全部的操作是使用Schlenk技术在干燥氩气下在热风枪干燥的玻璃器具中进行的。Ni(Xstb)3是在螺帽小瓶中在空气下在冰箱(-18℃)中存储的，除了Ni(4-tBustb)3，其存储在试验台上。全部络合物是在空气中称重的。无水溶剂是从合适的干燥剂中蒸馏的，并且在氩气下转移：THF，Et2O(Mg/蒽)，CH2Cl2，CH3CN(CaH2)，己烷，甲苯(Na/K)，Et3N，DMA，1，4-二
Figure BDA0003487304920000101
烷(MS)，CPME，NMP和tAmOH是以无水等级购买的，并且在MS上存储。无水K3PO4，NaOtBu和NaHMDS存储在Schlenk或者手套箱中。快速柱色谱法(Flash columnchromatography)：Merck硅胶60(40-63μm)。MS(EI)：Finnigan MAT 8200(70eV)。精确的质量测定：MAT 95(Finnigan)。NMR光谱是使用Bruker Avance VIII-300或者Bruker AvanceIII HD 400MHz分光计来记录的。1H NMR光谱是参考所用的氘化溶剂的残留质子。13C NMR光谱是内部参考NMR溶剂的D-偶合的13C共振。化学位移(δ)是相对于TMS(四甲基硅烷)以ppm给出的，和偶合常数(J)是以Hz提供的。19F NMR光谱是外部参考CFCl3的19F共振。31P NMR光谱是外部参考H3PO4的31P共振。
制备(E)-茋的通用程序
Figure BDA0003487304920000111
在装备有大的搅拌棒和回流冷凝器的三颈圆底烧瓶中将取代的苯甲醛(1当量)加入到THF(0.3M)中。将该溶液冷却到-78℃，并且逐滴加入TiCl4(1.25当量)。使得该反应升温到室温，并且搅拌10min。Zn粉末(2.5当量)是在2min内分为数个部分加入的。将该反应回流3h，然后使其冷却到室温。加入水(1.5×THF量)，随后加入HCl(0.1×THF量，3M)。将该反应搅拌5min，并且转移到分液漏斗。将含水层用MTBE(2×双倍THF量)萃取，将合并的有机层用饱和NaCl水溶液清洗和在MgSO4上干燥。将溶剂减压蒸发，并且将残留物进行柱色谱法。将净化的产物在高真空下干燥。
(E)-1，2-双(4-(三氟甲基)苯基)乙烷
Figure BDA0003487304920000112
根据通用程序由4-三氟甲基苯甲醛(11.0mL，14.0g，80.5mmol)，TiCl4(11.0mL，19.0g，100.3mmol，1.25当量)和Zn粉(13.0g，198mmol，2.5当量)来制备。柱色谱法：梯度己烷：MTBE(100：0-99：1)。
产率：8.44g，26.7mmol，66％；无色固体
(E)-1，2-双(4-(叔丁基)苯基)乙烯
Figure BDA0003487304920000113
根据通用程序由4-(叔丁基)苯甲醛(10.20ml，9.86g，60.8mmol，1当量)，TiCl4(20.0mL，34.6g，182.4mmol，3当量)和Zn粉(29.8g，456mmol，7.5当量)来制备。柱色谱法：梯度己烷：MTBE(50：1-20：1)。分光数据是根据文献。
产率：3.98g，13.6mmol，45％；无色固体
(E)-1，2-双(4-氟苯基)乙烷
Figure BDA0003487304920000121
根据通用程序由4-氟苯甲醛(1.30ml，1.50g，12.09mmol，1当量)，TiCl4(1.60mL，2.75g，14.50mmol，1.2当量)和Zn粉(1.98g，30.22mmol，2.5当量)来制备。柱色谱法：99：1(己烷：MTBE)。分光数据是根据文献。
产率：1.28g，5.91mmol，49％；无色固体
(E)-1，2-双(3，5-二甲基苯基)乙烷
Figure BDA0003487304920000122
根据通用程序由3，5-二甲基苯甲醛(5.01ml，5.00g，37.27mmol，1当量)，TiCl4(4.90mL，8.48g，44.72mmol，1.2当量)和Zn粉(6.10g，93.28mmol，2.5当量)来制备。柱色谱法：50：1(己烷：MTBE)。分光数据是根据文献。
产率：2960mg，18.63mmol，67％；无色固体
合成(E)-1，2-二-对甲苯基乙烯
Figure BDA0003487304920000131
将4-甲基苯乙烯(1.98mL，1.77g，15mmol，1当量)和二代Grubbs(9.4mg，0.015mmol，0.1mol％)溶解在DCM(3mL)中。将该反应回流3h，将溶剂在减压下蒸发，并且将固体通过柱色谱法净化(纯己烷)。分光数据是根据文献。
产率：1.1212g，5.38mmol，72％；无色固体
制备Ni(stb)3(1)
Figure BDA0003487304920000132
经由氩气筒向Schlenk管中加入Ni(CDT)(CDT＝1，5，9-反式，反式，反式-环十二碳三烯)(794mg，3.60mmol)，并且溶解在THF(7mL)中。将该溶液在氩气下过滤到保持于-78℃的Schlenk管中。将该滤饼用3mL的THF清洗。向单独的Schlenk管中加入反式茋(2.13g，11.87mmol，3.30当量)，并且进行一个真空/氩气循环。将该配体悬浮在THF(10mL)中，并且作为悬浮液转移到第一Schlenk管，随后是一个清洗(2mL THF)来确保定量转移。将该反应在-78℃搅拌10min，然后置于-5℃的冷却浴中，并且在那个温度搅拌12h。
将氩玻璃料(frit)冷却到-30℃，并且将该反应转移到所述玻璃料上。使得该混合物冷却1min，然后用正压氩气进行过滤。通过将氩气流送过该玻璃料来干燥该玻璃料上的固体。该固体然后转移到Schlenk管，并且在高真空下在室温进一步干燥来产生作为空气稳定的棕红色固体(1.07g，1.66mmol，46％)的1。
制备Ni(4-CF3stb)3(2)
Figure BDA0003487304920000141
经由氩气筒向Schlenk管中加入Ni(CDT)(CDT＝1，5，9-反式，反式，反式-环十二碳三烯)(610mg，2.76mmol)，并且将-78℃的新鲜Et2O(10mL)加入来悬浮该起始材料。向单独的Schlenk管中加入反式-pCF3-茋(2.28g，9.12mmol，3.15当量)，并且进行一个真空/氩气循环。将该配体悬浮在Et2O(10mL)中，并且作为悬浮液转移到第一Schlenk管，随后是几个清洗(3+2+2mL)来确保定量转移。将该反应置于-5℃的冷却浴中，并且在那个温度搅拌3h。
将氩玻璃料冷却到-30℃，并且将该反应转移到所述玻璃料上。使得该反应冷却1min，然后用正压氩气进行过滤。将该玻璃料上的固体用Et2O(3×2mL)清洗和通过将氩气流送过该玻璃料来干燥。该固体然后转移到Schlenk管，并且在高真空下在室温进一步干燥来产生作为空气稳定的红色固体(1.93g，1.92mmol，70％)的2。将该催化剂存储于冰箱中的空气下。
由Ni(acac)2制备Ni(4-CF3stb)3
Figure BDA0003487304920000142
向100mL的Schlenk管中经由氩气筒加入无水Ni(acac)2(904.4mg，3.52mmol)，和(E)-1，2-双(4-(三氟甲基)苯基)乙烷(3.50g，11.1mmol，3.14当量)。加入二乙醚(20mL)，并且将该溶液冷却到-20℃。将AlEt3(纯净)(1.10mL，7.5mmol，2.1当量)溶解在二乙醚(5mL)中。然后，将这个溶液在10min内逐滴加入到含有Ni(acac)2和茋配体的Schlenk中。将该反应在-20℃搅拌1小时，然后在干冰浴(-78℃)中冷却10分钟。将该悬浮液在冷却的(-78℃)氩玻璃料上过滤，这将产物留在玻璃料上。将该固体用二乙醚(2×2mL)清洗和在高真空下干燥。将Ni(Fstb)3作为红色固体(2.17g，2.16mmol，61％)的纯净形式进行分离。其它Ni(0)-络合物是按照上述方法制备的。
催化反应
5-(噻吩-3-基)嘧啶(13)
Figure BDA0003487304920000151
将Ni(4-CF3stb)3(2.0mg，0.002mmol，0.005当量)，5-溴嘧啶(64.5mg，0.406mmol)，噻吩-3-基硼酸(102.3mg，0.800mmol，2当量)，dppf(1.1mg，0.002mmol，0.005当量)和无水K3PO4(135mg，0.64mmol，1.5当量)置于螺帽小瓶中，其随后进行一个真空/氩气循环。加入1，4-二
Figure BDA0003487304920000153
烷(1mL)，并且将该反应加热到80℃持续8h。加入水，并且将含水层用10mL的Et2O萃取3次。将合并的有机层用MgSO4干燥和减压下蒸发。将粗产物进行柱色谱法(3：1-1：1；己烷：EtOAc)来产生作为白色固体(66.7mg，>99％)的分析纯形式的13。当在冰箱中将络合物2样品存储>100天之后，使用它作为预催化剂时获得了相同的产率。
4，5-二甲基-2-苯基吡啶(16)
Figure BDA0003487304920000152
将Ni(4-CF3stb)3(50.4mg，0.05mmol，0.1当量)置于压力气密的Schlenk管中(其是密封的)，并且进行了一个真空/氩气循环。将该Schlenk管转移到手套箱，加入PCy3(56.1mg，0.2mmol，0.4当量)，并且将该Schlenk从手套箱中再次取出。加入甲苯(3mL)，随后加入2，3-二甲基丁-1，3-二烯(226.3μL，164.3mg，2mmol，4当量)和苯甲腈(51.1μL，51.6mg，0.5mmol)。该Schlenk管是压力气密来密封，并且加热到130℃持续48h。减压下除去溶剂，并且将粗产物通过柱色谱法进行净化(9：1-5：1；己烷：EtOAc)来产生作为黄色油的16(76.7mg，0.419mmol，84％)。
3，4-二丙基-2-(吡啶-2-基甲基)异喹啉-1(2H)-酮(19)
Figure BDA0003487304920000161
向10-mL压力气密的Schlenk管中加入N-(吡啶-2-基甲基)苯甲酰胺(106.1mg，0.50mmol)，PPh3(52.5mg，0.20mmol，0.4当量)，4-辛炔(0.22mL，1.50mmol，3.0当量)和Ni(4 -CF3stb)3(50.4mg，0.05mmol，0.1当量)。加入干燥甲苯(2mL)，并且将该反应混合物置于170℃的预热油浴中和搅拌20h。在冷却到室温后，减压下除去溶剂。经由柱色谱法(1：1；己烷：EtOAc)净化粗残留物提供了作为黄色油的纯净19(151mg，0.47mmol，94％)。
4-(4-(三氟甲基)苯基)吗啉(22)
Figure BDA0003487304920000162
向12mL螺帽小瓶中加入Ni(4-CF3stb)3(27.2mg，0.027mmol，0.05当量)，SIPr·HCl(26.8mg，0.063mmol，0.116当量)和干燥CPME(1.5mL)。将4-氯苯并三氟化合物(72μL，0.540mmol，1.00当量)和吗啉(57μL，0.648mmol，1.20当量)加入该溶液。在将该溶液在室温搅拌15min的同时，所述混合物变成橙黄色的。然后加入NaOtBu(2M THF，543μL，1.080mmol，2.00当量)，然后将棕色的反应混合物在100℃的预热油浴中搅拌4h。在冷却到室温之后，减压下除去溶剂。粗残留物的柱色谱法(9：1；己烷：EtOAc)提供了作为无色固体的22(114mg，0.493mmol，91％产率)。
N-(4-甲氧基苯基)-2，5-二甲基苯胺(825)
Figure BDA0003487304920000163
向12mL螺帽小瓶中加入Ni(4-CF3stb)3(20.1mg，0.02mmol，0.02当量)，dppf(22.2mg，0.04mmol，0.04当量)和无水叔丁氧化钠(134.5mg，1.40mmol，1.40当量)。加入甲苯(2mL)，随后加入2-氯对二甲苯(0.134mL，1.00mmol，1.00当量)和对茴香胺(147.8mg，1.20mmol，1.20当量)。加入另外的甲苯(2mL)，并且将该小瓶置于130℃的预热油浴中，并且搅拌48h。在冷却到室温后，将该反应混合物用EtOAc稀释和加入水，并且分离所述层。将含水层用EtOAc萃取，并且将合并的有机层在MgSO4上干燥。将溶剂在减压下除去，并且将粗残留物经由柱色谱法净化(梯度：50：1-20：1；己烷：EtOAc)来提供作为橙色油的25(205.1mg，0.90mmol，90％产率)。
2-(2-(三氟甲基)苯基)-2H-色烯(28)
Figure BDA0003487304920000171
向12mL螺帽小瓶中加入Ni(4-CF3stb)3(58.6mg，0.05mmol，0.09当量)和PPh3(39.3mg，0.15mmol，0.27当量)。加入1，4-二
Figure BDA0003487304920000173
烷(1ml)，并且将该溶液搅拌5min。向50mL的Schlenk管中加入2-乙氧基-2H-色烯(98.9mg，0.56mmol)，(2-(三氟甲基)苯基)硼酸(189.9mg，1.00mmol，1.78当量)，二
Figure BDA0003487304920000174
烷(23mL)和t-AmOH(2mL)。催化剂+配体溶液转移两个第二Schlenk管，并且将该反应置于100℃的预热油浴中40min。使得该反应冷却和减压下蒸发溶剂。将残留物进行柱色谱法(纯己烷)来产生作为无色油的纯28(131.9mg，0.56mmol，85％)。
2-(1H-吲哚-3-基)乙基3-苯基丙酸酯(31)
Figure BDA0003487304920000172
向12mL螺帽小瓶中加入Ni(4-CF3stb)3(20.1mg，0.02mmol，0.1当量)，三联吡啶(4.7mg，0.02mmol，0.1当量)，苄基(3-苯基丙酰基)氨基甲酸叔丁酯(67.9mg，0.20mmol，1.00当量)和色醇(40.3mg，0.25mmol，1.25当量)。加入甲苯(0.2mL)，并且将该小瓶置于130℃的预热油浴中。在搅拌23h后，使得该溶液冷却到室温，并且将内容物用EtOAc和己烷转移到圆底烧瓶中。将溶剂在减压下除去，并且将粗残留物经由柱色谱法(7：1；己烷/EtOAc)净化来提供作为橙色油的31(38.5mg，0.13mmol，65％产率)。
2-甲基十一烷(34)
Figure BDA0003487304920000181
向12mL螺帽小瓶中加入Ni(4-CF3stb)3(10.0mg，0.010mmol，0.04当量)和2，6-双((R)-4-苯基-4，5-二氢
Figure BDA0003487304920000184
唑-2-基)吡啶(7.4mg，0.020mmol，0.08当量)。在氩气下加入DMA(0.4mL)，将该深蓝色溶液在室温搅拌10min，并且加入十四烷(用于GC分析的内部标准物，20μL，0.077mmol)。将该混合物在室温搅拌另外10min，并且加入正壬基溴化锌溶液(0.85M的DMA溶液，0.47mL，0.400mmol，1.57当量)和异丙基溴化物(24μL，0.256mmol，1.00当量)。将该反应混合物在60℃搅拌20小时后，通过GC-FID分析测定为58％产率的34。
1-乙烯基萘(37)
Figure BDA0003487304920000182
向螺帽小瓶中加入Ni(4-CF3stb)3(10.1mg，0.01mmol，0.05当量)，进行一个真空/氩气循环，并且将该小瓶转移到手套箱。加入Xantphos(5.8mg，0.01mmol，0.05当量)，并且将该小瓶从手套箱中取出。加入THF(150μL)，1-溴化萘(28.0μL，41.4mg，0.2mmol)和乙烯基溴化锌(1M的THF/NMP溶液，350μL，1.75当量)。将该反应加热到50℃持续5h和随后用EtOAc稀释。加入作为内部标准物的荚(25μL，21.6mg)，经由GC-FID分析测定为92％产率的37。
萘(40)
Figure BDA0003487304920000183
向12mL螺帽小瓶中加入2-(甲基硫)萘(87.2mg，0.50mmol，1.0当量)和Ni(4- CF3stb)3(50.4mg，0.05mmol，0.1当量)。加入正十二烷(用于GC分析的内部标准物，20μL，0.09mmol)，EtMe2SiH(0.13mL，0.98mmol，2.0当量)和甲苯(2mL)。将该小瓶置于90℃的预热油浴中，并且保持搅拌14小时。在冷却到室温后，将该混合物用EtOAc(4mL)稀释，并且经由GC-FID分析测定为91％产率的40。
1，2，3，4，5-五氟-6-(辛-4-烯-4-基)苯(43)
Figure BDA0003487304920000191
向螺帽小瓶中加入Ni(4-CF3stb)3(20.1mg，0.02mmol，0.1当量)IMes·HCl(6.8mg，0.02mmol，0.1当量)和无水NaHMDS(3.6mg，0.02mmol，0.1当量)。加入甲苯(1.5mL)，并且将该混合物搅拌5min。加入1，2，3，4，5-五氟苯(22.2μL，33.6mg，0.2mmol)和4-octin(44.0μL，33.1mg，0.3mmol，1.5当量)，并且使用甲苯(0.5mL)来清洗基底。将反应在室温搅拌3h，并且通过加入CH2Cl2来终止。将该混合物在二氧化硅塞上过滤，并且蒸发来干燥。加入α，α，α-三氟甲苯(24.6μL，29.2mg，0.2mmol，1.0当量)作为内部标准物，产率(90％)是通过19F NMR测定的。
如上所述，Ni催化领域长期存在的问题已经通过提供本发明的络合物作为Ni(0)预催化剂而得以解决，其模拟了Ni(COD)2的显著反应性，但是具有坚固、空气稳定和在开口烧瓶条件中易于处置的优点。这里，本发明人报道了二元Ni(0)-烯烃络合物的合成和表征，其满足了全部的这些需求，并且使用Ni催化无需使用复杂的Schlenk技术或者手套箱。本发明的Ni(0)-烯烃络合物Ni(R)3是模块化Ni(0)-烯烃络合物的一个独特的例子，其在空气下具有显著的稳定性，并且受益于它的16-电子构造带来的溶液中的高反应性。它的催化能力已经以Ni(COD)2的那些为基准，并且本发明人已经显示了Ni(R)3是在Ni催化的转变中是一个优异的预催化剂。不同于基于Ni(II)络合物的常规的空气稳定的前体，Ni(R)3的特征在于它在溶液中传递Ni(0)物质和提供离散的和明确的Ni(0)-配体络合物的固有能力。可以预期Ni(R)3作为Ni(0)预催化剂的显著性能将快速扩展到全部的Ni催化领域，因此能够容易设定和加速新反应性的发现。
(E)-戊-3-烯腈(45)
Figure BDA0003487304920000201
这种化合物是依照文献程序制备的，但是用络合物6代替了Ni(COD)2。向Schlenk管中加入Ni(4-tBustb)3(1.04g，1.11mmol，0.9mol％)和PPh3(2.91g，11.1mmol，9mol％)。加入2-甲基丁-3-烯腈(12.5ml，10.0g，123.3mmol，1当量)，将该反应加热到100℃持续3h。在使得该反应冷却到室温之后，将所述溶液打开到空气，并且用非干燥甲苯转移到圆底烧瓶。尝试进行蒸馏，但是由于产物和三种它的异构体的沸点接近而失败。将全部的部分与蒸馏残留物进行合并，并且加入CH2Br2(8.65mL，21.43g，123.3mmol，1当量)作为内部标准物。产率是通过NMR测定的：67％(6.70g，82.6mmol)。
α-烯烃C6-C22
Figure BDA0003487304920000202
这些化合物是采用文献程序制备的，但是用络合物6代替Ni(COD)2。将具有玻璃入口的50mL钢质高压釜设置在氩气下。向Schlenk管中加入Ni(4-tBustb)3(12.2mg，0.013mmol，1当量)，1-苯基-2-(三苯基-λ5-phosphanylidene)乙-1-酮(4.9mg，0.013mmol，1当量)和PPh3(3.4mg，0.013mmol，1当量)。将该固体溶解在甲苯(20mL)中，并且用注射器转移到高压釜。将该高压釜用5bar的乙烯气体加压，并且在25℃搅拌15h。该高压釜然后用60bar乙烯加压和加热到60℃持续45min。该反应表现出放热性能，这导致压力和温度上升，并且峰值为80bar和75℃内部温度。使得该高压釜达到室温，并且释放压力。加入1-十一碳烯(200μL，150mg)作为内部标准物，并且制备了GC样品(在二氧化硅塞上过滤，用戊烷洗提)。
GC分析结果：
#碳数 质量 mmol 所需周转量 mmol乙烯
6 72.0 0.856 3 2.57
8 125.1 1.115 4 4.46
10 97.1 0.692 5 3.46
12 83.4 0.495 6 2.97
14 70.8 0.361 7 2.53
16 65.5 0.292 8 2.34
18 68.1 0.270 9 2.43
20 55.0 0.196 10 1.96
22 52.9 0.171 11 1.88
总和 689.9 24.59
Ni(PPh3)2(4-tBustb)(48)
Figure BDA0003487304920000211
将Ni(4-tBustb)3(46.8mg，0.05mmol，1当量)和PPh3(52.4mg，0.2mmol，4当量)溶解在d8-甲苯(1mL)中，并且转移到NMR管。31P NMR分析显示1：1混合物，其是络合物48和2当量的游离PPh3。依照相同的程序，将Ni(COD)2(13.8mg，0.05mmol，1当量)和PPh3(52.4mg，0.2mmol，4当量)溶解在d8-甲苯(1mL)中，并且通过31P NMR进行分析。Ni(COD)(PPh3)2和Ni(PPh3)4的1：3混合物。
总结上面的内容，本发明提供了空气稳定的16-电子反式-烯烃-Ni(0)络合物的合成，其区别在于它们在支撑性茋的芳环中的取代基不同，和它们在不同的催化应用中的用途。这些取代基的系统性研究使得本发明人能够建立对于氧化的高稳定性的来源是优选在茋配体的对位上的取代基所推断的空间需要的结果。这个基本的观察被证明是一种具有显著的物理性能的优异的Ni(0)源。本发明络合物取决于它们在芳基残基上的实际取代，提供了更快的动力曲线，更宽的催化性能，并且已经在大部分应用中，在相同水平时在挑战性催化转变中表现出优于Ni(COD)2。本发明络合物与Ni(COD)2的反应性的高度类似性、宽的应用性、高的实践性和坚固性将在Ni催化领域获得快速应用。

Claims (11)

1.空气稳定的Ni(R)3-络合物，其中Ni表示Ni(0)，和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure FDA0003487304910000011
其中R1-R10可以是相同或者不同的，和选自H、Cl、Br、F、CN、C1-C6烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，
其中R11-R12可以是相同或者不同的，和选自H、C1-C6烷基、C3-C6环烷基、-O-C1-C6烷基或者-O-C3-C6环烷基，
条件是R1-R12中的至少一个不是氢。
2.根据权利要求1的空气稳定的Ni(R)3-络合物，
其中Ni表示Ni(0)，
其中R是相同或者不同的，和表示式(I)的反式茋；
其中在式(I)中，R1-R5中的至少一个和R6-R10中的至少一个是相同或者不同的，和选自Cl、Br、F、CN、C1-C8烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，和优选选自C1-C8烷基，其可以非必要地是支化的和/或用一个或多个卤素取代的，和其它的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H、C1-C8烷基、C3-C6环烷基、-O-C1-C8烷基或者-O-C3-C6环烷基。
3.根据权利要求1的空气稳定的Ni(R)3-络合物，
其中Ni表示Ni(0)，
其中R是相同或者不同的，和表示式(I)的反式茋：
其中在式(I)中，R3和R8是相同或者不同的，和选自C1-C8烷基，其可以非必要地用一个或多个卤素取代，和其余的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H、C1-C6烷基、-O-C1-C6烷基、C3-C6环烷基或者-O-C3-C6环烷基。
4.根据权利要求1的空气稳定的Ni(R)3-络合物，
其中Ni表示Ni(0)，
其中R是相同或者不同的，和表示式(I)的反式茋：
其中在式(I)中，R3和R8是相同或者不同的，和选自C1-C8全氟烷基，和其余的R1-R10是氢，和R11-R12可以是相同或者不同的，和选自H、C1-C6烷基、O-C1-C6烷基、C3-C6环烷基或者-O-C3-C6环烷基。
5.根据权利要求1的空气稳定的Ni(R)3-络合物，
其中Ni表示Ni(0)，
其中R是相同的，和表示式(I)的反式茋：
其中在式(I)中，R3和R8每个是C1-C8全氟烷基，和其它的R1-R10和R11-R12是氢。
6.根据权利要求1的空气稳定的Ni(R)3-络合物，
其中Ni表示Ni(0)，
其中R是相同的，和表示式(I)的反式茋：
其中在式(I)中，R3和R8每个是-CF3，和其它的R1-R10和R11-R12是氢。
7.制备空气稳定的Ni(R)3-络合物的方法，其中Ni表示Ni(0)和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure FDA0003487304910000031
其中R1-R10可以是相同或者不同的，和选自H、Cl、Br、F、CN、C1-C6烷基或者C3-C6环烷基，该烷基或者环烷基可以非必要地用一个或多个卤素取代，
其中R11-R12可以是相同或者不同的，和选自H、C1-C6烷基、C3-C6环烷基、-O-C1-C6烷基或者-O-C3-C6环烷基，
其中选自NiF2、NiCl2、NiBr2、NiI2、Ni(OTf)2、Ni(BF4)2、Ni(OTs)2、Ni(甘醇二甲醚)Cl2、Ni(甘醇二甲醚)Br2、Ni(二甘醇二甲醚)Cl2、Ni(二甘醇二甲醚)Br2、Ni(NO3)2、Ni(OR13)2(其中R13表示-C(O)-C1-C6-烷基，其是非必要地用一个或多个卤素取代的，优选用Cl或者F取代)、(乙酰基丙酮酸)2Ni、Ni(Ac)2或者其混合物的镍(II)化合物是在式Al(R14)3的烷基铝存在下，优选至少2当量，与式(I)的反式茋反应，优选至少3当量，其中R14可以是相同或者不同的，和选自C1-C6烷基或者C3-C6环烷基。
8.制备根据权利要求7的空气稳定的Ni(R)3-络合物的方法，其中式Al(R14)3的烷基铝选自Al(CH3)3或者Al(C2H5)3。
9.制备根据权利要求7或者8的空气稳定的Ni(R)3-络合物的方法，其中R表示权利要求2-6中任一项所定义的式(I)的反式茋。
10.根据权利要求1-6中任一项的空气稳定的Ni(R)3-络合物用作有机合成中的催化剂或者预催化剂的用途，其中：
Ni表示Ni(0)，和R可以是相同或者不同的，和表示式(I)的反式茋：
Figure FDA0003487304910000041
R1-R10可以是相同或者不同的，和选自H、Cl、Br、F、CN、C1-C6烷基或者C3-C6环烷基，其可以非必要地用一个或多个卤素取代，
R11-R12可以是相同或者不同的，和选自H、-O-C1-C6烷基、C1-C6烷基或者C3-C6环烷基，
非必要地，条件是R1-R12中的至少一个不是氢。
11.根据权利要求1-6中任一项的空气稳定的Ni(R)3-络合物用作有机合成中的催化剂的用途。
CN202080053726.5A 2019-07-30 2020-07-14 空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催化剂的用途 Pending CN114174312A (zh)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP19189236.3A EP3771707A1 (en) 2019-07-30 2019-07-30 Air-stable ni(0)-olefin complex and its use as catalyst and precatalyst
EP19189236.3 2019-07-30
DE102019214138 2019-09-17
DE102019214138.2 2019-09-17
PCT/EP2020/069898 WO2021018572A1 (en) 2019-07-30 2020-07-14 Air-stable ni(0)-olefin complexes and their use as catalysts or precatalysts

Publications (1)

Publication Number Publication Date
CN114174312A true CN114174312A (zh) 2022-03-11

Family

ID=71670231

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080053726.5A Pending CN114174312A (zh) 2019-07-30 2020-07-14 空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催化剂的用途

Country Status (11)

Country Link
US (1) US20220266232A1 (zh)
EP (1) EP3994113B1 (zh)
JP (1) JP2022542677A (zh)
KR (1) KR20220041864A (zh)
CN (1) CN114174312A (zh)
AU (1) AU2020321271B2 (zh)
BR (1) BR112021026648A2 (zh)
CA (1) CA3145230A1 (zh)
DE (1) DE202020005813U1 (zh)
IL (1) IL289931A (zh)
WO (1) WO2021018572A1 (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1320729A (fr) * 1959-12-22 1963-03-15 Studiengesellschaft Kohle Mbh Nouveaux complexes de métaux de transition et procédé pour leur préparation
US4017526A (en) * 1959-12-22 1977-04-12 Studiengesellschaft Kohle M.B.H. Metal complexes
CN108290829A (zh) * 2015-12-01 2018-07-17 科勒研究有限公司 用于催化可逆烯烃-腈相互转化的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1320729A (fr) * 1959-12-22 1963-03-15 Studiengesellschaft Kohle Mbh Nouveaux complexes de métaux de transition et procédé pour leur préparation
US4017526A (en) * 1959-12-22 1977-04-12 Studiengesellschaft Kohle M.B.H. Metal complexes
CN108290829A (zh) * 2015-12-01 2018-07-17 科勒研究有限公司 用于催化可逆烯烃-腈相互转化的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FISCHER, KARL ET AL.: "The catalytic conversion of olefins, VIII. Naked nickel as a catalyst for the transalkylation of aluminum trialkyls with α-olefins", 《ZEITSCHRIFT FUER NATURFORSCHUNG, TEIL B: ANORGANISCHE CHEMIE, ORGANISCHE CHEMIE》, vol. 39, no. 8, pages 1011 - 1021 *
LUKAS NATTMANN ET AL.: "An air-stable binary Ni(0)–olefin catalyst", 《NATURE CATALYSIS》, vol. 3, pages 6 - 13, XP093039377, DOI: 10.1038/s41929-019-0392-6 *

Also Published As

Publication number Publication date
WO2021018572A1 (en) 2021-02-04
JP2022542677A (ja) 2022-10-06
IL289931A (en) 2022-03-01
AU2020321271A1 (en) 2022-02-17
KR20220041864A (ko) 2022-04-01
EP3994113B1 (en) 2024-07-03
BR112021026648A2 (pt) 2022-05-10
AU2020321271B2 (en) 2024-07-11
US20220266232A1 (en) 2022-08-25
CA3145230A1 (en) 2021-02-04
EP3994113A1 (en) 2022-05-11
DE202020005813U1 (de) 2022-09-06

Similar Documents

Publication Publication Date Title
Hoshimoto et al. One-Pot, Single-Step, and Gram-Scale Synthesis of Mononuclear [(η6-arene) Ni (N-heterocyclic carbene)] Complexes: Useful Precursors of the Ni0–NHC Unit
Consorti et al. On the Use of Non‐Symmetrical Mixed PCN and SCN Pincer Palladacycles as Catalyst Precursors for the Heck Reaction
Kakiuchi et al. Room-temperature regioselective C− H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates
Yoon et al. Metal Triflate‐Catalyzed Regio‐and Stereoselective Friedel–Crafts Alkenylation of Arenes with Alkynes in an Ionic Liquid: Scope and Mechanism
Sidera et al. Formation of quaternary centers by copper-catalyzed asymmetric conjugate addition of alkylzirconium reagents.
Lee et al. Well-defined palladium (0) complexes bearing N-heterocyclic carbene and phosphine moieties: efficient catalytic applications in the Mizoroki–Heck reaction and direct C–H functionalization
Norton et al. A superior precursor for palladium (0)-based cross-coupling and other catalytic reactions
Katayama et al. (Z)-Selective cross-dimerization of arylacetylenes with silylacetylenes catalyzed by vinylideneruthenium complexes
Maestre et al. A fully recyclable heterogenized Cu catalyst for the general carbene transfer reaction in batch and flow
Li et al. Nickel-catalyzed substitution reactions of propargyl halides with organotitanium reagents
Aydemir et al. trans-and cis-Ru (II) aminophosphine complexes: Syntheses, X-ray structures and catalytic activity in transfer hydrogenation of acetophenone derivatives
Baratta et al. Convenient syntheses of novel ruthenium catalysts bearing N-heterocyclic carbenes
WO2014034906A1 (ja) α－フルオロアクリル酸エステルの製造方法
Morales-Morales et al. Highly efficient and regioselective couplings of aryl halides to olefins catalyzed by a palladium complex with a hybrid phosphorus–sulfur ligand
EP1885669A1 (en) Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions
Motolko et al. Rigid NON-donor pincer ligand complexes of lutetium and lanthanum: synthesis and hydroamination catalysis
O'Shaughnessy et al. Chiral biarylamido/anisole complexes of yttrium in enantioselective aminoalkene hydaroamination/cyclisation
Pal et al. Recent advances in carbosilylation of alkenes and alkynes
Hung et al. Olefin Reactivities toward the Ph-PW (CO) 5 Phosphinidene
CN106573946B (zh) 络合物
Wu et al. FeCl3‐and GaCl3‐Catalyzed Dehydrative Coupling Reaction of Chromone‐Derived Morita‐Baylis‐Hillman Alcohols with Terminal Alkynes
US10065976B2 (en) Titanium (IV) compounds and methods of forming heterocyclic compounds using same
CN114174312A (zh) 空气稳定的Ni(0)-烯烃络合物以及它们作为催化剂或者预催化剂的用途
US20030109380A1 (en) Catalytic boronate ester synthesis from boron reagents and hydrocarbons
Sun et al. 3 (5)-Pyrazolyl substituted triphenylphosphines as ligands for the palladium catalyzed Heck reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination