WO2012040853A1 - Complexes de métaux du groupe 5 utiles pour la fonctionnalisation par amine et procédé de synthèse pour leur fabrication - Google Patents

Complexes de métaux du groupe 5 utiles pour la fonctionnalisation par amine et procédé de synthèse pour leur fabrication Download PDF

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WO2012040853A1
WO2012040853A1 PCT/CA2011/050609 CA2011050609W WO2012040853A1 WO 2012040853 A1 WO2012040853 A1 WO 2012040853A1 CA 2011050609 W CA2011050609 W CA 2011050609W WO 2012040853 A1 WO2012040853 A1 WO 2012040853A1
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substituted
unsubstituted
group
independently
branched
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Laurel L. Schafer
Jean Michel P. Lauzon
Rashidat O. Ayinla
Patrick Eisenberger
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The University Of British Columbia
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
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    • 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
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    • 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
    • C07C213/08—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 not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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    • 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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    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of 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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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
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    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/12—1,4-Thiazines; Hydrogenated 1,4-thiazines not condensed with other rings
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    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • 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
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/58—Tantalum
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    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the present invention pertains to catalysts useful for amine functionalization.
  • R 1 and R 2 are each independently H; a Ci ⁇ C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group, wherein R 1 and R 2 can be bonded together thereby forming, together with the nitrogen atom and the carbon atom to which they are bound, a cyclic moiety; and each R 3 is independently a C] - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group.
  • R 1 and R 2 are independently H; a Cj - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl or a substituted or unsubstituted heterocyclic group, wherein R 1 and R 2 can be bonded together thereby forming, together with the nitrogen atom and the carbon atom to which they are bound, a cyclic moiety, and wherein the R 1 substituents are bound, or "tethered", to one another, the R 2 substituents are bound to one another, or an R 1 substituent is bound to an R 2 substituent;
  • a metallaaziridine complex having the structure of Formula lb:
  • X is a halo substituent, such as CI, F, I or Br;
  • M, X, R 1 , R 2 , R 3 , s and n are as defined above.
  • the bond formation comprises o-alkylation of the secondary amine.
  • the secondary amine containing moiety and the second moiety are in the same molecule, in the case of an intramolecular reaction.
  • the secondary amine containing moiety and the second moiety are in different molecules, in the case of an intermolecular reaction.
  • X is a halo substituent
  • R 1 and R 2 are independently H; a d - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group, wherein R 1 and R 2 can be bonded together thereby forming, together with the nitrogen atom and the carbon atom to which they are bound, a cyclic moiety; and
  • M is a group 5 metal
  • a process for synthesizing an a-amino acid, an o-amino acid derivative, a /3-amino acid, a -amino acid derivative, a ⁇ - amino acid, or a ⁇ -amino acid derivative comprising reacting a secondary amine of Formula V with a compound of Formula VI
  • n 1 or 2;
  • R' is independently a - C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; a substituted or unsubstituted heterocyclic group; or NR 2 ;
  • each R 4 is independently H, a Ci - C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl or a substituted or unsubstituted heterocyclic group;
  • Figure 3 graphically depicts the results of comparing catalytic reactivities of two Ta(amidate) complexes (— ⁇ — 0.01M complex 18:— ⁇ — 0.025M complex 18:— ⁇ — 0.05M complex 18:—A— 0.05M complex 1).
  • alkynyl refers to an unsaturated, straight or branched chain hydrocarbon group containing at least one triple bond which can be unsubstituted or optionally substituted with one or more substituents.
  • heteroaryl refers to an aryl that includes from 1 to 10, in other embodiments 1 to 4, heteroatoms selected from oxygen, nitrogen and sulfur, which can be substituted or unsubstituted.
  • substituted refers to the structure having one or more substituents.
  • a substituent is an atom or group of bonded atoms that can be considered to have replaced one or more hydrogen atoms attached to a parent molecular entity.
  • Possible substituents include any atom or group that does not inhibit the desired reaction. Examples of substituents include aliphatic, halogen, arylcarbonyloxy, alkoxycarbonyloxy,
  • olefins include, but are not limited to, substituted or unsubsituted 1-propene, 1 -butene, 1-pentene, 1- hexene, and 1-octene and substituted or unsubstitued norbornene.
  • R 1 and R 2 are each independently H; a Cj - C 2 5, or a Ci - Ci 2, substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group (for example, a heteroaryl), wherein R 1 and R 2 can be bonded together thereby forming, together with the nitrogen atom and the carbon atom to which they are bound, a cyclic moiety;
  • R' is independently a Q - C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; a substituted or unsubstituted heterocyclic group; or NR 3 2 ; and each R 3 is independently a C - C25, or a Ci - C12, substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group (for example, a heteroaryl).
  • the metallaaziridine complex of Formula Ic encompasses complexes having all three amidate binding motifs (i.e., bidentate, as depicted, or monodentate monodentate manner through either the oxygen or the nitrogen). For convenience only the bidentate form is shown.
  • one or more of the R 1 and R 2 substituents comprises a chiral group such that the resulting complex can be used as a catalyst in enantioselective reactions.
  • Formula la has the following structure:
  • M is a group 5 metal, such as Ta, Nb, or V;
  • n 1 or 2;
  • each R 3 is independently a Ci - C25, or a Ci - C 12 , substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group (for example, a heteroaryl).
  • each R 3 is independently a Cj - C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group.
  • R' is independently a Ci - C 25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group.
  • group 5 metal- amidate complexes having the structure of Formula Ila in which R' is NR 3 2 :
  • M is a group 5 metal, such as Ta, Nb or V;
  • the group 5 metal- amidate complex of Formula lla encompasses complexes having all three amidate binding motifs (i.e., bidentate, as depicted, or monodentate monodentate manner through either the oxygen or the nitrogen). For convenience only the bidentate form is shown.
  • one or more of the R 1 and R 2 substituents comprises a chiral group such that the resulting complex can be used as a catalyst in enantioselective reactions.
  • R 1 and R 2 substituents comprises a chiral group such that the resulting complex can be used as a catalyst in enantioselective reactions.
  • the corresponding non- halo group 5 metal-amidate complexes can be prepared using the same synthetic process in which the starting metal amide does not include a halo bound to the metal atom.
  • the group 5 metal amidate complexes described herein can be prepared using a synthesis that includes salt metathesis.
  • halo group 5 metal-amidate complexes can be prepared according to Scheme 4 set out below: Scheme 4
  • the group 5 metal complexes are capable of effecting the general reaction depicted in Scheme 5, wherein an alpha positioned hydrogen atom on an amine is added across an olefin.
  • the carbon positions marked with asterisks may be chiral in the product:
  • the catalytic -alkylation of secondary amines described above is an improvement over current methods used for synthesizing amines.
  • the catalytic reaction is 100% atom economic since all of the substrate atoms are in the product, thus avoiding any waste or unwanted by-products.
  • the use of the group 5 metal amidate complexes of Formula 1 provides the ability to control the reaction by selecting amidate ligands with different steric and/or electronic characteristics. It has been found that the catalytic a-alkylation reactions metal amidate complexes are more susceptible to changes in the steric bulk of the amidate ligands than the electronic effects, however, both characteristics can be used to provide a means for controlling the catalytic reaction.
  • N-substituted heterocycle is:
  • Saturated N-Heterocycles are privileged structural elements found in a wide variety of sophisticated molecules used in therapeutics and agrochemicals. Consequently, the rapid and selective construction of functionalized, saturated N-heterocycles from simple, inexpensive, readily available chemicals is critical in an industrial context. In addition, the development of "green" technologies in synthesis is an urgent goal with respect to transformations with 100% atom efficiency, high selectivity (chemo-, regio-, and stereoselectivity) and high chemical yields. Recently, group 4 and group 5 based catalyst systems have been successfully used in functionalizing the sp 3 C-H bond a to 1° and 2° amines.
  • Ta(amidate) complexes 20 and 22 which were synthesized and characterised as described in Example 4 above.
  • EXAMPLE 7 Tantalum Amidate Complexes in the Efficient Synthesis of 3- Amino Acids.
  • Figure 5 is an ORTEP diagram of the crystal structure of metal complex 30.
  • This Example demonstrates the successful use of a group 5 metal complex as described herein in the synthesis of a four-membered and a five-membered heterocycle.
  • the reaction can be performed in one pot, thereby eliminating the need for isolation and/or purification of the intermediate hydroaminoalkylation product. It should be noted that an overall 55% yield of the four-membered azetidine product was obtained using the one-pot synthesis even without optimization of the reaction conditions.
  • This general synthetic process has application in the production of various heterocycles. The following table summarizes some general applications of this synthetic process:

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Abstract

La présente invention concerne des complexes de métaux du Groupe 5 utiles pour la fonctionnalisation par amine et un procédé de synthèse pour leur fabrication. L'invention concerne des complexes halo métal du Groupe 5 - amidate ayant la structure de Formule I : I dans laquelle : M représente un métal du Groupe 5, tel que Ta, Nb ou V ; X représente un substituant halo, tel que Cl, F, I ou Br ; n = 1 ou 2 ; s = 1 ou 2 ; R1 et R2 représentent chacun indépendamment H ; un alkyle linéaire, ramifié ou cyclique, substitué ou non substitué, en C1-C25 ; ou des groupes aryle ou hétérocycliques substitués ou non substitués ; R' représente indépendamment un alkyle linéaire, ramifié ou cyclique, substitué ou non substitué, en C1-C25 ; un aryle substitué ou non substitué ; un groupe hétérocyclique substitué ou non substitué ; ou NR3 2 ; et chaque R3 représente indépendamment un alkyle linéaire, ramifié ou cyclique, substitué ou non substitué, en C1-C25 ; un aryle substitué ou non substitué ; ou un groupe hétérocyclique substitué ou non substitué ; ainsi qu'un procédé de synthèse de ces complexes. L'invention concerne également les complexes métallaaziridines correspondants. Le complexe métallique de la Formule I, et le complexe métallaaziridine correspondant sont utiles en tant que catalyseur dans l'α-alkylation d'amines secondaires, et, en conséquence, concerne également des procédés d'utilisation du complexe métallique de Formule I, et le complexe métallaaziridine correspondant dans l'α-alkylation d'amines secondaires. Cette invention concerne également des procédés d'utilisation des complexes non halo métal du Groupe 5 - amidate correspondants et les complexes métallaaziridines dans l'α-alkylation d'hétérocycles.
PCT/CA2011/050609 2010-09-28 2011-09-28 Complexes de métaux du groupe 5 utiles pour la fonctionnalisation par amine et procédé de synthèse pour leur fabrication WO2012040853A1 (fr)

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US11034707B2 (en) 2017-05-26 2021-06-15 The University Of British Columbia Group 5 metal complexes for catalytic amine functionalization
US11555107B2 (en) 2018-05-23 2023-01-17 The University Of British Columbia Amine functionalized polymers and methods of preparation

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11034707B2 (en) 2017-05-26 2021-06-15 The University Of British Columbia Group 5 metal complexes for catalytic amine functionalization
US11555107B2 (en) 2018-05-23 2023-01-17 The University Of British Columbia Amine functionalized polymers and methods of preparation
US11795315B2 (en) 2018-05-23 2023-10-24 The University Of British Columbia Group 5 metal complexes for producing amine-functionalized polyolefins

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