N-heterocyclic carbene complexes of metal imido alkylidenes and metal OXO alkylidenes, and the use of same

Patent metadata

Field	Value
Publication number	US-10072036-B2
Application number	US-201515306521-A
Country	US
Kind code	B2
Filing date	Apr 24, 2015
Priority date	Apr 25, 2014
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

First claim

The invention claimed is:

1. An N-heterocyclic carbene complex of one of the general formulae I-IV

wherein:
A 1 is NR 2 or PR 2 , A 2 is CR 2 R 2′ , NR 2 , PR 2 , O or S, A 3 is N or P, C is a carbene carbon atom,
the ring B is an unsubstituted or a mono- or polysubstituted 5- to 7-membered ring which, as well as A 1 , A 2 and/or A 3 , may contain further heteroatoms in the form of nitrogen, phosphorus, oxygen or sulfur and wherein the substituents may have the definition described for R 2 ,
the substituents R 2 and R 2′ are independently H, a linear, partly cyclic or branched C 1 -C 18 -alkyl, a linear, partly cyclic or branched C 2 -C 18 -alkenyl, a C 3 -C 12 -cycloalkyl, a linear, partly cyclic or branched C 6 -C 100 -polyoxaalkyl, a C 5 -C 14 -aryl or -heteroaryl radical, a C 5 -C 14 -aryloxy, a linear, partly cyclic or branched C 1 -C 18 -perfluoroalkyl, a linear, partly cyclic or branched C 1 -C 18 -perchloroalkyl, a linear, partly cyclic or branched part-fluorinated C 1 -C 18 -alkyl, a linear, partly cyclic or branched part-chlorinated C 1 -C 18 -alkyl, a per- or part-fluorinated C 6 -C 14 -aryl, a per- or part-chlorinated C 5 -C 14 -aryl radical, and, when A 1 and A 2 are each NR 2 or PR 2 , R 2 may be the same or different, or
R 2 and R 2′ together are a linear or branched C 1 -C 18 -alkylene,
M in the formulae I, II, III and IV is Cr, Mo or W,
X 1 and X 2 in formulae I to IV are the same or different and are selected from the group consisting of halogen, C 1 -C 18 carboxylates, C 1 -C 18 -alkoxides, fluorinated C 1 -C 18 alkoxides, C 1 -C 18 mono- or polyhalogenated carboxylates, unsubstituted or mono- or polysubstituted C 6 -C 18 mono-, bi- or terphenoxides, trifluoromethanesulfonate, and non-coordinating anions, where the substituents on the mono-, bi- or terphenoxides, can be halogen or may have the same definition as R 2 ,
Y is oxygen, sulfur, an N-adamantyl, an N-tert-butyl, a C 6 -C 14 —N-aryl radical, where the aryl radical may be mono- or polysubstituted by halogen, a linear or branched C 1 -C 18 alkyl, a linear or branched C 1 -C 18 alkyloxy or an unsubstituted or substituted phenyl radical wherein the substituents have the same definition as R 2 ,
Z is a linear, partly cyclic or branched C 1 -C 10 -alkyleneoxy, a linear, partly cyclic or branched C 1 -C 10 -alkylenethio, a linear, partly cyclic or branched C 1 -C 10 -alkylene-NR 2 , a C 6 -C 10 -aryleneoxy, a per- or part-fluorinated C 6 -C 14 -aryleneoxy, a per- or part-chlorinated C 6 -C 14 -aryleneoxy, a per- or part-brominated C 6 -C 14 -aryleneoxy, a C 6 -C 14 -arylenethio, a per- or part-fluorinated C 6 -C 14 -arylenethio, a per- or part-chlorinated C 6 -C 14 -arylenethio, a per- or part-brominated C 6 -C 14 -arylenethio, C 6 -C 14 -arylene-NR 2 , a per- or part-fluorinated C 6 -C 14 -arylene-NR 2 , a per- or part-chlorinated C 6 -C 14 -arylene-NR 2 , a per- or part-brominated C 6 -C 14 -arylene-NR 2 , a C 6 -C 14 -arylene-PR 2 , a per- or part-fluorinated C 6 -C 14 -arylene-PR 2 , a per- or part-chlorinated C 6 -C 14 -arylene-PR 2 , a per- or part-brominated C 6 -C 14 -arylene-PR 2 , a carboxyl, a thiocarboxyl or a dithiocarboxyl group, and
R 1 and R 1′ in the formulae I to IV are independently H, aliphatic, aromatic radical, linear or branched C 1 -C 18 alkyl group, tert-butyl, CMe 2 Ph group, unsubstituted or mono- or polysubstituted C 6 -C 14 -aryl group, where the substituents have the definitions given for R 2 , 2-(2-propoxy)phen-1-yl; 2-methoxyphen-1-yl; 2,4,5-trimethoxyphenyl; or ferrocenyl.

2. An N-heterocyclic carbene complex as claimed in claim 1 , wherein the ring B is a heterocycle selected from the group comprising 1,3-disubstituted imidazol-2-ylidenes, 1,3-disubstituted imidazolin-2-ylidenes, 1,3-disubstituted tetrahydro-pyrimidin-2-ylidenes, 1,3-disubstituted diazepin-2-ylidenes, 1,3-disubstituted dihydrodiazepin-2-ylidenes, 1,3-disubstituted tetrahydrodiazepin-2-ylidenes, N-substituted thiazol-2-ylidenes, N-substituted thiazolin-2-ylidenes, N-substituted triazol-2-ylidenes, mono- or polysubstituted dihydrotriazol-2-ylidenes, mono- or polysubstituted triazolin-2-ylidenes, N-substituted thiadiazol-2-ylidenes, mono- or polysubstituted thiadiazolin-2-ylidenes and mono- or polysubstituted tetrahydrotriazol-2-ylidenes.

3. An N-heterocyclic carbene complex as claimed in claim 1 , wherein the ring B is bonded covalently via a spacer group to a solid support.

4. An N-heterocyclic carbene complex as claimed in claim 3 , wherein the solid support is a polymeric support, and the spacer group is a C 1 -C 20 -α,ω-dioxaalkylene or a C 1 -C 20 -alkyleneoxy group.

5. An N-heterocyclic carbene complex as claimed in claim 3 , wherein the solid support is an inorganic support, and the spacer group is an alkyl-Si(O) 3 or an alkyl-SiR(O) 2 group in which R has the same definition as R 2 .

6. An N-heterocyclic carbene complex as claimed in claim 1 , wherein R 1 in formulae I, II, III or IV is t-butyl, an unsubstituted or substituted phenyl, ferrocenyl or CMe 2 Ph, R 1′ in addition to H may have all the definitions mentioned for R 1 and substituents on the phenyl may have the same definition as R 2 .

7. An N-heterocyclic carbene complex as claimed in claim 1 , wherein the non-coordinating anions as X 1 and X 2 are selected from tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate, tetrakis(penta-fluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)-aluminate, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate.

8. A method of conducting an olefin metathesis reaction, the method including:
contacting a substrate for the olefin methathesis reaction with a catalyst, wherein the catalyst is an N-heterocyclic carbene complex according to claim 1 .

9. The method as claimed in claim 8 , wherein the olefin metathesis reaction is an asymmetric or desymmetrizing ring-closing metathesis, a cross-metathesis, a ring-opening cross-metathesis, a (cross-)ene-yne metathesis, a ring-closing ene-yne metathesis, a cross-ene-diyne metathesis, a tandem ring-opening-ring-closing metathesis, a ring-opening metathesis polymerization (ROMP), a 1-alkyne polymerization, an acyclic diene metathesis polymerization (ADMET) or a cyclopolymerization of α,ω-diynes.

10. The method as claimed in claim 8 , wherein the olefin metathesis reaction is an olefinolysis of fatty acid esters.

11. The method as claimed in claim 10 , wherein the olefinolysis of fatty acid esters comprises the olefinolysis of vegetable oils and fats.

12. The method as claimed in claim 11 , wherein the vegetable oils are selected from the group consisting of castor oil, palm oil, and coconut oil.

13. The method as claimed in claim 12 , wherein the vegetable oils are combined with at least one of ethylene and butene.

14. The method as claimed in claim 8 , wherein the catalyst is a compound of formula II or IV and the method further comprises:
dissolving the compound of formula II or IV in an organic solvent (I) or in an ionic liquid to form a solution,
applying the solution in the form of a thin film to a support material,
introducing the support material including the thin film into a reaction vessel, and
introducing a substrate into the reaction vessel, wherein the substrate is dissolved in a solvent (II) that is immiscible with the organic solvent (I) or the ionic liquid.

15. The method as claimed in claim 14 , wherein the ionic liquid used is 1,3-dimethyl-imidazolium salt, 1,2,3-trimethylimidaz

Assignees

• Univ Stuttgart

Inventors

• Buchmeiser Michael R
• Sen Suman
• Schowner Roman

Classifications

• C08G2261/419

  Acyclic diene metathesis [ADMET] · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G61/12

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C07F11/00 Primary

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title