Organoruthenium carbide complexes as precatalysts for olefin metathesis

Patent metadata

Field	Value
Publication number	US-11554365-B2
Application number	US-202217677102-A
Country	US
Kind code	B2
Filing date	Feb 22, 2022
Priority date	Sep 18, 2019
Publication date	Jan 17, 2023
Grant date	Jan 17, 2023

Abstract

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II):

Wherein X, L, R 1 , R 2 , R 3 , R 4 , R 5 , Ar 1 and Ar 2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of formula (I) or formula (II) as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

First claim

What is claimed is:

1. A compound of formula II:

wherein:
X is chlorine, bromine or iodine;
L is PR 3 , where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C 5 -C 10 )alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;
R 2 and R 3 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 1 -C 6 )alkyl, (C 6 -C 10 )aryl, methoxy, ethoxy, linear or branched (C 1 -C 6 )alkoxy, (C 6 -C 10 )aryloxy, —NHCO(C 1 -C 6 )alkyl, —NHCO-perfluoro(C 1 -C 6 )alkyl, —SO 2 N((C 1 -C 6 )alkyl) 2 and —NO 2 ; or
R 2 and R 3 taken together with the carbon atom to which they are attached to form a (C 3 -C 7 )cycloalkyl ring;
R 4 and R 5 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 1 -C 6 )alkyl;
Ar 2 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl.

2. The compound according to claim 1 , wherein:
X is chlorine or iodine;
each R 2 , R 3 , R 4 and R 5 is independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and phenyl;
Ar 2 is substituted phenyl; and
L is PR 3 , where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl.

3. The compound according to claim 1 , wherein:
X is chlorine;
R 2 and R 3 taken together with the carbon atom to which they are attached to form a cyclopentyl, cyclohexyl or cycloheptyl ring;
each R 4 and R 5 is independently selected from the group consisting of hydrogen, methyl, ethyl and iso-propyl;
Ar 2 is selected from the group consisting of phenyl, 2-methylphenyl,
2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl,
2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and
L is tri(isopropyl)phosphine or tricyclohexylphosphine.

4. The compound according to claim 1 , wherein:
X is chlorine;
each R 2 , R 3 , R 4 and R 5 independently is methyl or ethyl;
Ar 2 is selected from the group consisting of phenyl, 2,4-dimethylphenyl,
2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl,
2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and
L is tricyclohexylphosphine.

5. The compound according to claim 1 , wherein:
X is iodine;
each R 2 , R 3 , R 4 and R 5 independently is methyl or ethyl;
Ar 2 is selected from the group consisting of 2,6-dimethylphenyl,
2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl and 2,6-diisopropylphenyl; and
L is tricyclohexylphosphine.

6. The compound according to claim 1 , which is:

1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide dichloride.

7. The compound according to claim 1 , which is:

1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide dichloride.

8. The compound according to claim 1 , which is:

1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide diiodide.

9. The compound according to claim 1 , which is:

1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide diiodide.

10. The compound according to claim 1 , which is:

1-(2,6-diisopropylphenyl)-3,3-dimethyl-2λ 2 -azaspiro[4.5]decylidene-triisopropylphosphine ruthenium carbide dichloride.

11. The compound according to claim 1 , which is:

1-(2,6-diisopropylphenyl)-3,3-dimethyl-2λ 2 -azaspiro[4.5]decylidene-triisopropylphosphine ruthenium carbide diiodide.

12. The compound according to claim 1 , which is:

1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide dichloride.

13. The compound according to claim 1 , which is:

1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide diiodide.

14. A process for carrying out a metathesis reaction of olefins, comprising contacting at least one olefin with the compound of claim 1 as a precatalyst.

15. The process according to claim 14 , wherein the metathesis reaction is carried out in an organic solvent.

16. The process according to claim 15 , wherein the organic solvent is selected from the group consisting of dichloromethane, dichloroethane, toluene, ethyl acetate and a mixture in any combination thereof.

17. The process according to claim 14 , wherein the metathesis reaction is carried out in the presence of a chemical activator.

18. The process according to claim 17 , wherein the chemical activator is a Bronsted or Lewis acid or a halo-derivative of alkane or silane.

19. The process according to claim 14 , wherein the metathesis reaction is carried out in the presence of a photoacid generator.

20. The process according to claim 14 , wherein the metathesis reaction is carried out in the presence of a thermal acid generator.

Assignees

• Apeiron Synthesis Sa
• Promerus Llc

Inventors

• Gawin Rafał
• Burtovyy Oleksandr
• Rhodes Larry F

Classifications

• B01J2540/54

  Quaternary phosphonium groups · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• C07D207/02

  with only hydrogen or carbon atoms directly attached to the ring nitrogen atom · CPC title

• C07D235/00

  Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings · CPC title