Metathesis catalysts and methods thereof

Patent metadata

Field	Value
Publication number	US-9315604-B2
Application number	US-201414248712-A
Country	US
Kind code	B2
Filing date	Apr 9, 2014
Priority date	Apr 9, 2013
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.

First claim

The invention claimed is:

1. A compound of formula I:

wherein:
M is molybdenum or tungsten;
R 1 is an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each of R 2 and R 3 is independently R′, —OR′, —SR′, —N(R′) 2 , —OC(O)R′, —SOR′, —SO 2 R′, —SO 2 N(R′) 2 , —C(O)N(R′) 2 , —NR′C(O)R′, or —NR′ SO 2 R′;
n is 0-4;
r is 0-2;
each R 4 is independently hydrogen or optionally substituted C 1-4 aliphatic;
each R 5 is independently a monodentate ligand, or two R 5 are optionally taken together to form a bidentate ligand;
each R′ is independently hydrogen or an optionally substituted group selected from C 1-6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or:
two R′ groups on the same nitrogen atom are optionally taken together with the nitrogen atom to form an optionally substituted 3-8 membered, saturated, partially unsaturated, or aryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and

2. The compound of claim 1 , wherein one of R 2 and R 3 is hydrogen and the other is —C(Me) 3 or —C(Me) 2 Ph.

3. The compound of claim 1 , wherein r is 0.

4. The compound of claim 1 , wherein r is 1 and R 5 is R′CN.

5. The compound of claim 1 , wherein

and each R 4 is methyl.

6. The compound of claim 1 , wherein R 1 is selected from

7. The compound of claim 1 , wherein the compound is Mo(NC 6 F 5 )(CHCMe 2 Ph)(Me 2 Pyr)(DFTO), Mo(NC 6 F 5 )(CHCMe 2 Ph)(Me 2 Pyr)(DFTO)(MeCN), Mo(N(2,6-Me 2 C 6 H 3 ))(CHCMe 2 Ph)(Me 2 Pyr)(DFTO), or Mo(N(2,6-Me 2 C 6 H 3 ))(CHCMe 2 Ph)(Me 2 Pyr)(DFTO)(MeCN), wherein Me 2 Pyr is 2,5-dimethylpyrrolyl, and DFTO is 2,6-(C 6 F 5 ) 2 C 6 H 3 O—.

8. The compound of claim 1 , wherein the compound is isolated.

9. The compound of claim 3 , wherein the compound is isolated.

10. A method for preparing a compound of claim 1 , comprising steps of:
1) providing a compound having the structure of formula III:

2) providing a first ligand or ligand precursor; and
3) reacting the compound of formula III with a second ligand or ligand precursor in the presence of the first ligand or ligand precursor, wherein the second ligand or ligand precursor having the structure of formula IV:

or a salt thereof.

11. The method of claim 10 , wherein a first ligand or ligand precursor is R 5 .

12. The method of claim 10 , wherein a first ligand or ligand precursor is CH 3 CN.

13. A method for performing a metathesis reaction, comprising providing a compound of claim 1 .

14. The method of claim 13 , wherein the metathesis reaction is ring-opening metathesis polymerization (ROMP), and the ROMP polymer product is greater than about 95% isotactic and greater than about 95% cis.

15. A compound of formula II:

wherein
M is molybdenum or tungsten;
R 1 is an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
R 2′ and R 3′ are taken together with their intervening metal atoms to form an optionally substituted 3-8 membered saturated or partially unsaturated ring having, in addition to the intervening metal atom, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
m is 0-3;
each of p and q is independently 0-5, and at least one of p and q is not 0;
r is 0-2;
each of R x , R y and R z is independently an electron-withdrawing group;
each R 5 is independently a monodentate ligand, or two R 5 are optionally taken together to form a bidentate ligand; and
each R′ is independently hydrogen or an optionally substituted group selected from C 1-6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or:
two R′ groups on the same nitrogen atom are optionally taken together with the nitrogen atom to form an optionally substituted 3-8 membered, saturated, partially unsaturated, or aryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

Assignees

• Massachusetts Inst Technology

Inventors

• Schrock Richard Royce
• Yuan Jian

Classifications

• C08G2261/3324

  derived from norbornene · CPC title

• C08G61/08

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

• C08G2261/3325

  derived from other polycyclic systems · CPC title

• C08G2261/21

  Stereochemical aspects · CPC title

• B01J31/34

  of chromium, molybdenum or tungsten · CPC title