Metathesis catalysts and methods thereof
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.
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.
16. The compound of claim 15 , wherein R 2′ and R 3′ are taken together with M to form an optionally substituted 3-membered ring.
17. The compound of claim 8 , wherein the compound has the structure of formula II-a:
18. The compound of claim 17 , wherein
19. The compound of claim 17 , wherein the compound is isolated.
20. The compound of claim 15 , wherein r is 0.
21. The compound of claim 15 , wherein r is 1 and R 5 is R′CN.
22. The compound of claim 15 , wherein
23. The compound of claim 15 , wherein R 1 is selected from
24. The compound of claim 15 , wherein the compound is Mo(NC 6 F 5 )(CH 2 CH 2 )(DFTO) 2 , Mo(NC 6 F 5 )(CH 2 CH 2 )(DCMNBD)(DFTO) 2 , Mo(NC 6 F 5 )(CH 2 CH 2 CH 2 )(DFTO) 2 , or Mo(NC 6 F 5 )(CH 2 CH 2 CH 2 CH 2 )(DFTO) 2 , wherein DFTO is 2,6-(C 6 F 5 ) 2 C 6 H 3 O—.
25. A method for preparing a compound of claim 15 , comprising:
reacting a compound having the structure of formula V:
with an olefin, 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′;
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.
26. A method for preparing a compound of claim 15 , wherein the compound has the structure 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;
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 1-2;
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;
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,
comprising:
reacting a compound having the structure of formula II-a:
with a ligand or ligand precursor comprising or having the structure of R 5 .
27. A method for performing a metathesis reaction, comprising providing a compound of claim 15 .
28. The method of claim 27 , 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.
29. A compound of formula V:
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′;
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.
30. The compound of claim 29 , wherein
31. The compound of claim 30 , wherein the compound is Mo(NC 6 F 5 )(CHCMe 2 Ph)(DFTO) 2 , Mo(NC 6 F 5 )(CHCH═C(Me)Ph)(DFTO) 2 , Mo(N(2,6-i-Pr 2 C 6 H 3 ))(CHCMe 2 Ph)(DFTO) 2 , Mo(N(2,6-Me 2 C 6 H 3 ))(CHCMe 2 Ph)(DFTO) 2 , or Mo(N(1-adamantyl))(CHCMe 2 Ph)(DFTO) 2 , wherein DFTO is 2,6-(C 6 F 5 ) 2 C 6 H 3 O—.
32. A method for performing a metathesis reaction, comprising providing a compound of claim 29 .
33. The method of claim 32 , wherein the metathesis reaction is ring-opening metathesis polymerization (ROMP), and the ROMP product is greater than about 95% cis and greater than about 95% isotactic.