Catalysts for (E)-selective olefin metathesis

Patent metadata

Field	Value
Publication number	US-9701704-B2
Application number	US-201615074545-A
Country	US
Kind code	B2
Filing date	Mar 18, 2016
Priority date	Mar 20, 2015
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in (E)-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

First claim

What is claimed is:

1. A compound represented by Formula (IV):

wherein:
M is a Group 8 transition metal;
R V1 , R V2 , R V3 , R V4 and R V5 are independently hydrogen, substituted branched C 1 -C 6 alkyl, C 4 -C 10 cycloalkyl, substituted C 4 -C 10 cycloalkyl, C 4 -C 10 heteroatom-containing cycloalkyl, substituted C 4 -C 10 heteroatom-containing cycloalkyl, C 5 -C 14 aryl, or substituted C 5 -C 14 aryl;
R 11 , R 12 , R 11a and R 12a are independently hydrogen, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 alkoxy, substituted C 1 -C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide;
X 1 and X 2 are independently halogen;
L 2 and L 3 are neutral electron donor ligands, wherein L 2 and/or L 3 may be linked with R 1 or R 2 to form one or more cyclic groups;
n is 0 or 1;
m is 0, 1, or 2;
k is 0 or 1;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
at least one of R V1 , R V2 , R V3 , R V4 or R V5 is represented by a group selected from:

“a” represents 0, 1, 2, 3, 4 or 5; and
R is substituted C 1 -C 6 alkyl, C 1 -C 6 alkyl, substituted C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl or halogen.

2. The compound according to claim 1 , wherein
M is Ru;
n is 0;
m is 0;
k is 1;
X 1 and X 2 are independently halogen;
L 2 is a neutral electron donor ligand; and
R 11 , R 12 , R 11a and R 12a are independently hydrogen.

3. The compound according to claim 2 , wherein:
R V1 , R V2 , R V3 , R V4 and R V5 are independently hydrogen or substituted branched C 1 -C 6 alkyl; and at least one of R V1 , R V2 , R V3 , R V4 or R V5 is represented by a group selected from:

4. The compound according to claim 3 , wherein:
R V1 , R V2 , R V3 and R V4 are independently hydrogen;
X 1 and X 2 are independently chloride;
L 2 is PCy 3 ;
R 1 is hydrogen;
R 2 is phenyl;
R V5 is

 and
“a” is 0.

5. The compound according to claim 3 , wherein the compound is in a racemic isomeric form, a meso isomeric form, or a mixture of the racemic and meso isomeric forms.

6. The compound according to claim 1 , wherein the compound is in a racemic isomeric form, a meso isomeric form, or a mixture of the racemic and meso isomeric forms.

7. The compound according to claim 1 , wherein the compound is:

8. The compound according to claim 7 , wherein the compound is in a racemic isomeric form, a meso isomeric form, or a mixture of the racemic and meso isomeric forms.

9. A compound represented by Formula (VII):

wherein:
M is Ru or Os;
R V1 , R V2 , R V3 , R V4 and R V5 are independently hydrogen, substituted branched C 1 -C 6 alkyl, C 4 -C 10 cycloalkyl, substituted C 4 -C 10 cycloalkyl, C 4 -C 10 heteroatom-containing cycloalkyl, substituted C 4 -C 10 heteroatom-containing cycloalkyl, C 5 -C 14 aryl, or substituted C 5 -C 14 aryl;
R 11 , R 12 , R 11a and R 12a are independently hydrogen, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 alkoxy, substituted C 1 -C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide;
X 1 and X 2 are independently halogen;
Y is a heteroatom selected from N, O, S, or P;
R 5 , R 6 , R 7 , and R 8 are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate;
n is 0, 1, or 2;
Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl; and at least one of R V1 , R V2 , R V3 , R V4 or R V5 is represented by a group selected from:

“a” represents 0, 1, 2, 3, 4 or 5; and
R is substituted C 1 -C 6 alkyl, C 1 -C 6 alkyl, substituted C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl or halogen.

10. The compound according to claim 5 wherein:
M is Ru;
X 1 and X 2 are each chloride;
Y is O;
R 5 , R 6 , R 7 , and R 8 are each hydrogen;
n is 1;
Z is iso-propyl;
R V1 , R V2 , R V3 and R V4 are independently hydrogen;
R 11 , R 12 , R 11a and R 12a are independently hydrogen;
R V5 is

 and
“a” represents 0.

11. The compound according to claim 9 , wherein the compound is:

12. The compound of according to claim 11 , wherein the compound is in a racemic isomeric form, a meso isomeric form, or a mixture of the racemic and meso isomeric forms.

13. A method for performing a metathesis reaction comprising, contacting at least one olefin with a compound of Formula (IV) or Formula (VII), wherein:
the compound of Formula (IV) is represented by

wherein:
M is a Group 8 transition metal;
R V1 , R V2 , R V3 , R V4 and R V5 are independently hydrogen, substituted branched C 1 -C 6 alkyl, C 4 -C 10 cycloalkyl, substituted C 4 -C 10 cycloalkyl, C 4 -C 10 heteroatom-containing cycloalkyl, substituted C 4 -C 10 heteroatom-containing cycloalkyl, C 5 -C 14 aryl, or substituted C 5 -C 14 aryl;
R 11 , R 12 , R 11a and R 12a are independently hydrogen, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 alkoxy, substituted C 1 -C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide,
X 1 and X 2 are independently halogen;
L 2 and L 3 are neutral electron donor ligands, wherein L 2 and/or L 3 may be linked with R 1 or R 2 to form one or more cyclic groups;
n is 0 or 1;
m is 0, 1, or 2;
k is 0 or 1;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
at least one of R V1 , R V2 , R V3 , R V4 or R V5 is represented by a group selected from:

“a” represents 0, 1, 2, 3, 4 or 5; and
R is sub

Assignees

• California Inst Of Techn

Inventors

• Lee Choon Woo
• Grubbs Robert H
• Guzman Pablo E
• Ahmed Tonia S
• Montgomery T Patrick

Classifications

• B01J31/2208

  Oxygen, e.g. acetylacetonates · CPC title

• B01J31/2278

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

• B01J2531/821

  Ruthenium · CPC title

• B01J31/122

  Metal aryl or alkyl compounds · CPC title

• C08G2261/3322

  derived from cyclooctene · CPC title