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US 2010/0144969 A1Published application
Isoselective polymerization of epoxides
AssigneeCornell University
InventorsGeoffrey W. Coates, Wataru Hirahata
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Abstract
The present invention provides novel bimetallic complexes and methods of using the same in the isoselective polymerization of epoxides. The invention also provides methods of kinetic resolution of epoxides. The invention further provides polyethers with high enantiomeric excess that are useful in applications ranging from consumer goods to materials.
Claims117
A bimetallic complex of formula I:
- wherein:
- M is a metal atom;
- X is a nucleophile;
- n is an integer from 0 to 2, inclusive each occurrence of L1, L2, Y1, and Y2 is independently —O—, —P(R′)2—, ═NR′—, or —N(R′)2—;
- each occurrence of
- is an optionally substituted moiety selected from the group consisting of C2-12 aliphatic, C7-12 arylalkyl;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- each occurrence of
- is an optionally substituted moiety selected from the group consisting of C7-12 arylalkyl;
- 6-10-membered aryl;
- and 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- represents a single bond directly attached to an aryl or heteroaryl ring of each
- each occurrence of R′ is hydrogen or an optionally substituted moiety selected from the group consisting of a C3-C14 carbocycle, a C6-C10 aryl group, a C3-C14 heterocycle, and a C5-C10 heteroaryl group;
- or an optionally substituted C2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NRy—, —N(Ry)C(O)—, —C(O)N(Ry)—, —OC(O)N(Ry)—, —N(Ry)C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO2—, —C(═S)—, —C(═NRy)—, —C(═NORy)— or —N═N—;
- or
- two R′ are taken together with their intervening atoms to form a monocyclic or bicyclic 5-12-membered ring;
- wherein a substituent may comprise one or more organic cations;
- and
- each occurrence of Ry is independently hydrogen or an optionally substituted C1-6 aliphatic group.
18 more elements
A polymer of formula:
- wherein:
- Ra is an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- and
- each of Rb and Rc is independently hydrogen or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- wherein any of (Ra and Rc), (Rb and Rc), and (Ra and Rb) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
- optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle,
- optionally substituted C6-C10 aryl, and optionally substituted C5-C10 heteroaryl;
- wherein the enantiomeric excess of the polymer is greater than 90%.
13 more elements
A polymer of formula:
- wherein:
- Ra is an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- and
- each of Rb and Rc is independently hydrogen or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- wherein any of (Ra and Rc), (Rb and Rc), and (Ra and Rb) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
- optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle,
- optionally substituted C6-C10 aryl, and optionally substituted C5-C10 heteroaryl;
- wherein the isotacticity of the polymer is greater than 90%.
13 more elements
A method of polymerization, the method comprising:
- a) providing a prochiral epoxide of formula:
- wherein:
- Ra is an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- and
- each of Rb and Rc is independently hydrogen or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
- C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- 6-10-membered aryl;
- 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
- and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
- wherein any of (Ra and Rc), (Rb and Rc), and (Ra and Rb) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
- optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle,
- optionally substituted C6-C10 aryl, and optionally substituted C5-C10 heteroaryl;
- and
- b) treating the epoxide with a bimetallic catalyst under suitable conditions to form a polymer of formula:
15 more elements
Dependencies are inferred from the claim text.