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US 9,315,604 B2Granted
Metathesis catalysts and methods thereof
AssigneeMassachusetts Institute of Technology
InventorsRichard Royce Schrock, Jian Yuan
Life of this patent
Estimating the term…
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.
Claims33
A compound of formula I:
- wherein:
- M is molybdenum or tungsten;
- R1 is an optionally substituted group selected from C1-20 aliphatic, C1-20 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 R2 and R3 is independently R′, —OR′, —SR′, —N(R′)2, —OC(O)R′, —SOR′, —SO2R′, —SO2N(R′)2, —C(O)N(R′)2, —NR′C(O)R′, or —NR′ SO2R′;
- n is 0-4;
- r is 0-2;
- each R4 is independently hydrogen or optionally substituted C1-4 aliphatic;
- each R5 is independently a monodentate ligand, or two R5 are optionally taken together to form a bidentate ligand;
- each R′ is independently hydrogen or an optionally substituted group selected from C1-6 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
9 more elements
A compound of formula II:
- wherein
- M is molybdenum or tungsten;
- R1 is an optionally substituted group selected from C1-20 aliphatic, C1-20 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;
- R2′ and R3′ 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 Rx, Ry and Rz is independently an electron-withdrawing group;
- each R5 is independently a monodentate ligand, or two R5 are optionally taken together to form a bidentate ligand;
- and
- each R′ is independently hydrogen or an optionally substituted group selected from C1-6 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.
10 more elements
A compound of formula V:
- wherein:
- M is molybdenum or tungsten;
- R1 is an optionally substituted group selected from C1-20 aliphatic, C1-20 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 R2 and R3 is independently R′, —OR′, —SR′, —N(R′)2, —OC(O)R′, —SOR′, —SO2R′, —SO2N(R′)2, —C(O)N(R′)2, —NR′C(O)R′, or —NR′ SO2R′;
- 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 Rx, Ry and Rz is independently an electron-withdrawing group;
- each R5 is independently a monodentate ligand, or two R5 are optionally taken together to form a bidentate ligand;
- and
- each R′ is independently hydrogen or an optionally substituted group selected from C1-6 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.
10 more elements
Dependencies are inferred from the claim text.