Organoruthenium carbide complexes as precatalysts for olefin metathesis

Patent metadata

Field	Value
Publication number	US-11291983-B2
Application number	US-202017024778-A
Country	US
Kind code	B2
Filing date	Sep 18, 2020
Priority date	Sep 18, 2019
Publication date	Apr 5, 2022
Grant date	Apr 5, 2022

Abstract

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II):Wherein X, L, R1, R2, R3, R4, R5, Ar1 and Ar2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of the 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 the formula I:

wherein:
X is chlorine, bromine or iodine;
L is PR 3 , where each 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 1 is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
Ar 1 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; and
with the proviso that when X is chlorine, R 1 is not 2,4,6-trimethylphenyl.

2. The compound according to claim 1 , wherein:
X is chlorine or iodine;
R 1 and Ar 1 are both 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 1 and Ar 1 are independently 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;
R 1 and Ar 1 are independently 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;
R 1 and Ar 1 are independently 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 selected from the group consisting of:

1,3-bis(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide diiodide;

1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide dichloride;

1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide diiodide.

7. 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.

8. The process according to claim 7 , wherein the metathesis reaction is carried out in an organic solvent.

9. The process according to claim 8 , wherein the organic solvent is selected from the group consisting of dichloromethane, dichloroethane, toluene, ethyl acetate and a mixture in any combination thereof.

10. The process according to claim 7 , wherein the metathesis reaction is carried out in the presence of a chemical activator.

11. The process according to claim 7 , wherein the chemical activator is a Bronsted or Lewis acid or a halo-derivative of alkane or silane.

Assignees

• Apeiron Synthesis Sa
• Promerus Llc

Inventors

• Gawin Rafał
• Burtovyy Oleksandr
• Rhodes Larry F

Classifications

• B01J2531/821

  Ruthenium · CPC title

• C07C6/06

  at a cyclic carbon-to-carbon double bond · CPC title

• 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} · CPC title

• 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 · CPC title

• B01J31/2273 Primary

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title