US2010144969A1PendingUtilityA1
Isoselective polymerization of epoxides
Est. expiryAug 17, 2027(~1.1 yrs left)· nominal 20-yr term from priority
C08G 65/226B01J 31/2208C08G 65/266C07D 303/22C08G 65/12B01J 2231/14C08G 65/223B01J 2531/0216B01J 2531/845C07F 15/065C07D 407/12C08G 65/10C08G 65/04C08G 65/105C07D 303/16C08G 65/22C08G 59/70C08G 65/14C07D 303/04B01J 31/1805B01J 2531/0205
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Claims
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.
Claims
exact text as granted — not AI-modified1 . 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 L 1 , L 2 , Y 1 , and Y 2 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 C 2-12 aliphatic, C 7-12 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 C 7-12 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 C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— 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 R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group.
2 . The bimetallic complex of claim 1 , wherein M is a main group metal.
3 . The bimetallic complex of claim 1 , wherein M is selected from the group consisting of a transition metal from group 5-12, inclusive, boron and aluminum.
4 . The bimetallic complex of claim 1 , wherein M is selected from the lanthanides.
5 . The bimetallic complex of claim 3 , wherein M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Ti, Al, Zr, Hf, and Ni.
6 . The bimetallic complex of claim 5 , wherein M is Co.
7 . The bimetallic complex of any one of claims 1 to 6 , wherein the complex contains an element having axial chirality.
8 . The bimetallic complex of claim 7 , wherein the element having axial chirality is contained in the portion of formula I having the formula:
9 . The bimetallic complex of claim 7 , wherein the axial chirality results from hindered rotation of the molecule about bond B1 indicated in the formula:
10 . The bimetallic complex of claim 1 , wherein the complex is of formula I-a:
wherein:
each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—;
each occurrence of R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group;
each occurrence of R 1 and R 2 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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; or
R 1 and R 2 are taken together with their intervening atoms to form an optionally substituted 4-14-membered carbocycle, an optionally substituted 4-14-membered heterocycle, an optionally substituted 6-10-membered aryl group or an optionally substituted 5-10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur ring; and
each occurrence of R 3 and R 4 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R Y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R, —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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.
11 . The bimetallic complex of claim 1 , wherein the complex is of formula I-b:
wherein:
each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—;
each occurrence of R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group; and
each occurrence of R 5 , R 5a , and R 5b is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 adjacent R 5 , R 5a , or R 5b groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms.
12 . The bimetallic complex of claim 1 , wherein the complex is of formula I-c:
wherein:
each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—;
each occurrence of R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group;
each occurrence of R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 adjacent R 6 , R 7 , R 8 , or R 9 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms.
13 . The bimetallic complex of claim 1 , wherein the complex is of formula II:
wherein:
each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—;
each occurrence of R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group;
each occurrence of R 1 and R 2 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R Y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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; or
R 1 and R 2 are taken together with their intervening atoms to form an optionally substituted 4-14-membered carbocycle, an optionally substituted 4-14-membered heterocycle, an optionally substituted 6-10-membered aryl group or an optionally substituted 5-10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur ring; and
each occurrence of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R Y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 adjacent R 6 , R 7 , R 8 , or R 9 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms.
14 . The bimetallic complex of claim 13 , wherein M is Co.
15 . The bimetallic complex of claim 1 or 13 , wherein n is 0.
16 . The bimetallic complex of claim 1 or 13 , wherein n is 1.
17 . The bimetallic complex of claim 1 or 13 , wherein n is 2.
18 . The bimetallic complex of claim 1 or 13 , wherein X is halogen.
19 . The bimetallic complex of claim 18 , wherein X is Cl.
20 . The bimetallic complex of claim 13 , wherein Q is optionally substituted C 5-10 aliphatic.
21 . The bimetallic complex of claim 20 , wherein Q is optionally substituted C 6-8 aliphatic.
22 . The bimetallic complex of claim 21 , wherein Q is optionally substituted 1,2-cyclohexyl.
23 . The bimetallic complex of claim 22 , wherein Q is (R,R)-1,2-cyclohexyl when the bond between the biaryl linkage is of S chirality.
24 . The bimetallic complex of claim 22 , wherein Q is (S,S)-1,2-cyclohexyl when the bond between the biaryl linkage is of R chirality.
25 . The bimetallic complex of claim 13 , wherein R 1 and R 2 are taken together with their intervening atoms to form a 6-10-membered aryl group, 4-14-membered carbocycle, or 5-10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur ring.
26 . The bimetallic complex of claim 25 , wherein R 1 and R 2 are taken together with their intervening atoms to form a 6-10-membered aryl ring.
27 . The bimetallic complex of claim 26 , wherein R 1 and R 2 are taken together with their intervening atoms to form a 6-membered aryl ring.
28 . The bimetallic complex of claim 27 , wherein R 1 and R 2 are taken together with their intervening atoms to form:
29 . The bimetallic complex of claim 25 , wherein R 1 and R 2 are taken together with their intervening atoms to form:
30 . The bimetallic complex of claim 13 , wherein each of R 3 , R 4 , R 5 , R 6 , and R 8 is hydrogen.
31 . The bimetallic complex of claim 13 , wherein each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is hydrogen.
32 . The bimetallic complex of claim 13 , wherein one or more of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is substituted with an organic cation.
33 . The bimetallic complex of claim 32 , wherein the organic cation is a quaternary ammonium group.
34 . The bimetallic complex of claim 32 , wherein each organic cation is complexed with X, wherein X is a nucleophile.
35 . The bimetallic complex of claim 34 , wherein X is 2,4-dinitrophenolate anion.
36 . The bimetallic complex of claim 13 , wherein R 7 and R 9 are independently optionally substituted groups selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur.
37 . The bimetallic complex of claim 36 , wherein R 7 and R 9 are independently an optionally substituted C 1-6 aliphatic group.
38 . The bimetallic complex of claim 37 , wherein R 7 and R 9 are t-butyl.
39 . The bimetallic complex of claim 1 or 13 , wherein the complex is racemic.
40 . The bimetallic complex of claim 1 or 13 , wherein the complex is non-racemic.
41 . The bimetallic complex of claim 1 or 13 , wherein the complex possesses axial symmetry.
42 . The bimetallic complex of claim 1 or 13 , wherein the complex is a catalyst.
43 . The bimetallic complex of claim 13 , wherein the complex is of formula II-a:
44 . The bimetallic complex of claim 43 , wherein the complex is of formula II-b:
45 . The bimetallic complex of claim 43 , wherein the complex is selected from:
46 . The bimetallic complex of claim 13 , wherein the complex is of formula II-c:
47 . A polymer of formula:
wherein:
R a is an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 R b and R c is independently hydrogen or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 (R a and R c ), (R b and R c ), and (R a and R b ) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
optionally substituted C 3 -C 14 carbocycle, optionally substituted C 3 -C 14 heterocycle,
optionally substituted C 6 -C 10 aryl, and optionally substituted C 5 -C 10 heteroaryl;
wherein the enantiomeric excess of the polymer is greater than 90%.
48 . The polymer of claim 47 , wherein the polymer comprises a copolymer of two different repeating units where R a , R b , and R c of the two different repeating units are not all the same.
49 . The polymer of claim 47 , wherein the polymer comprises a copolymer of three or more different repeating units wherein R a , R b , and R c of each of the different repeating units are not all the same as R a , R b , and R c of any of the other different repeating units.
50 . The polymer of any one of claims 47 to 49 , wherein the polymer is a random copolymer.
51 . The polymer of any one of claims 47 to 49 , wherein the polymer is a tapered copolymer.
52 . The polymer of any one of claims 47 to 49 , wherein the polymer is a block copolymer.
53 . The polymer of claim 47 , containing a bimetallic complex of claim 1 .
54 . The polymer of claim 47 , comprising residue of a bimetallic complex of claim 1 .
55 . The polymer of claim 54 , further comprising salt of an organic cation and X.
56 . The polymer of claim 47 , wherein R c is hydrogen.
57 . The polymer of claim 47 , wherein R b is hydrogen.
58 . The polymer of claim 47 , wherein R ip and R c are both hydrogen.
59 . The polymer of claim 58 , wherein R a is optionally substituted C 1-12 aliphatic.
60 . The polymer of claim 58 , wherein R a is optionally substituted C 1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur.
61 . The polymer of claim 58 , wherein R a is optionally substituted 6-10-membered aryl.
62 . The polymer of claim 58 , wherein R a is optionally substituted 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
63 . The polymer of claim 58 , wherein R a is selected from methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl, trifluoromethyl,
or any two or more of the above.
64 . The polymer of claim 63 , wherein R a is trifluoromethyl.
65 . The polymer of claim 63 , wherein R a is
66 . The polymer of any one of claims 47 to 65 , wherein the enantiomeric excess of a polymer chain comprising the polymer decreases from one end of the polymer chain to the other end of the polymer chain.
67 . The polymer of claim 66 wherein the decrease in the enantiomeric excess from one end of the polymer to the second end of the polymer is gradual.
68 . The polymer of any one of claims 47 to 65 , wherein the enantiomeric excess of the polymer is greater than 95%.
69 . The polymer of claim 68 , wherein the enantiomeric excess of the polymer is greater than 97%.
70 . The polymer of claim 69 , wherein the enantiomeric excess of the polymer is greater than 98%.
71 . The polymer of claim 70 , wherein the enantiomeric excess of the polymer is greater than 99%.
72 . A polymer of formula:
wherein:
R a is an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 R b and R c is independently hydrogen or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 (R a and R c ), (R b and R c ), and (R a and R b ) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
optionally substituted C 3 -C 14 carbocycle, optionally substituted C 3 -C 14 heterocycle,
optionally substituted C 6 -C 10 aryl, and optionally substituted C 5 -C 10 heteroaryl;
wherein the isotacticity of the polymer is greater than 90%.
73 . The polymer of any one of claims 47 to 65 , wherein the isotacticity of a polymer chain comprising the polymer is greater near one end of the polymer chain than near the other end of the polymer chain.
74 . The polymer of any one of claims 47 to 65 , wherein the isotacticity of a polymer chain comprising the polymer decreases from one end of the polymer chain to the other end of the polymer chain.
75 . The polymer of any one of claims 47 to 65 , wherein the polymer is optically inactive with m-dyad content greater than 80%.
76 . The polymer of any one of claims 47 to 65 , wherein the polymer is optically inactive with m-dyad content greater than 90%.
77 . The polymer of any one of claims 47 to 65 , wherein the polymer is optically inactive with m-dyad content greater than 95%.
78 . The polymer of any one of claims 47 to 65 , wherein the polymer is optically inactive with m-dyad content greater than 99%.
79 . A method of polymerization, the method comprising:
a) providing a prochiral epoxide of formula:
wherein:
R a is an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 R b and R c is independently hydrogen or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 (R a and R c ), (R b and R c ), and (R a and R b ) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of:
optionally substituted C 3 -C 14 carbocycle, optionally substituted C 3 -C 14 heterocycle,
optionally substituted C 6 -C 10 aryl, and optionally substituted C 5 -C 10 heteroaryl; and
b) treating the epoxide with a bimetallic catalyst under suitable conditions to form a polymer of formula:
80 . The method of claim 79 , wherein the bimetallic catalyst is a bimetallic complex of any one of claims 1 to 46 .
81 . The method of claim 79 , further comprising a step, after step (a), of adding at least one additional epoxide having the formula
wherein each of the additional epoxide has a structure different from the structure of the epoxide provided in step (a) such that the polymer formed in step (b) is a co-polymer of two or more epoxides.
82 . The method of claim 79 , wherein the bimetallic catalyst is of formula II:
wherein:
M is a main group metal;
each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C 3 -C 14 carbocycle, a C 6 -C 10 aryl group, a C 3 -C 14 heterocycle, and a C 5 -C 10 heteroaryl group; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—;
each occurrence of R y is independently hydrogen or an optionally substituted C 1-6 aliphatic group;
each occurrence of R 1 and R 2 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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; or
R 1 and R 2 are taken together with their intervening atoms to form an optionally substituted 4-14-membered carbocycle, an optionally substituted 4-14-membered heterocycle, an optionally substituted 6-10-membered aryl group or an optionally substituted 5-10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur ring; and
each occurrence of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR y , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted group selected from the group consisting of C 1-12 aliphatic; C 1-12 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 adjacent R 6 , R 7 , R 8 , or R 9 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms.
83 . The method of claim 82 , wherein n is 0.
84 . The method of claim 82 , wherein n is 1.
85 . The method of claim 82 , wherein n is 2.
86 . The method of claim 82 , wherein X is halogen.
87 . The method of claim 82 , wherein X is Cl.
88 . The method of claim 79 , wherein suitable conditions comprise one or more co-catalysts.
89 . The method of claim 88 , wherein the co-catalyst is selected from the group consisting of an amine, a phosphonium salt, an ammonium salt, an arsonium salt, and a combination of any two or more of the above.
90 . The method of claim 88 , wherein the co-catalyst is PPN-X, where X is a nucleophile.
91 . The method of claim 90 , wherein the co-catalyst is PPNOAc.
92 . The method of claim 79 or 82 , wherein the enantiomeric excess of the polymer is greater than 90%.
93 . The method of claim 79 or 82 , wherein the enantiomeric excess of the polymer is greater than 95%.
94 . The method of claim 79 or 82 , wherein the enantiomeric excess of the polymer is greater than 97%.
95 . The method of claim 79 or 82 , wherein the enantiomeric excess of the polymer is greater than 98%.
96 . The method of claim 79 or 82 , wherein the enantiomeric excess of the polymer is greater than 99%.
97 . The method of claim 79 or 82 , wherein the polymerization is enantioselective.
98 . The method of claim 79 or 82 , wherein the method is a kinetic resolution.
99 . The method of claim 79 or 82 , wherein the polymerization is living.
100 . The method of any one of claims 79 to 99 , further comprising the step of recovering unreacted epoxide, wherein the recovered epoxide is enantiomerically enriched.
101 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 50%.
102 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 75%.
103 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 90%.
104 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 95%.
105 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 97%.
106 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 98%.
107 . The method of claim 100 , wherein the enantiomeric excess of the recovered epoxide is greater than 99%.
108 . A material suitable for food packaging comprising a polymer of any one of claims 47 to 78 .
109 . An oil resistant material comprising a polymer of any one of claims 47 to 78 .
110 . A material suitable for electronics casing comprising a polymer of any one of claims 47 to 78 .
111 . A material suitable for packaging consumer goods comprising a polymer of any one of claims 47 to 78 .
112 . The material of any one of claims 108 to 111 , wherein the material is a film.
113 . A material suitable for chiral chromatographic media comprising a polymer of any one of claims 47 to 78 .
114 . A material suitable for polymeric reagents comprising a polymer of any one of claims 47 to 78 .
115 . A material suitable for polymeric catalysts comprising a polymer of any one of claims 47 to 78 .
116 . The material of any one of claims 108 to 111 , wherein the material is extruded.
117 . The material of any one of claims 108 to 111 , wherein the material is thermoformed.Join the waitlist — get patent alerts
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