Catalysts and methods for ring opening metathesis polymerization
The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.
1. A poly(dicyclopentadiene) polymer, wherein the polymer is greater than 95% syndiotactic as determined by 13 C NMR.
2. The polymer of claim 1 , wherein double bonds in the polymer backbone is greater than 90% cis as determined by 13 C NMR.
3. The polymer of claim 1 , wherein double bonds in the polymer backbone is greater than 95% cis as determined by 13 C NMR.
4. The polymer of claim 1 , wherein M n of the polymer is greater than about 5,000.
5. A composition comprising:
the polymer of claim 1 , and a tungsten-containing compound.
6. The composition of claim 5 , wherein the tungsten-containing compound is a compound of formula I:
wherein:
R 1 is —C(R 1a ) 3 ;
each R 1a is independently an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl 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 or polycyclic 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 1a groups are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:
three R 1a groups are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 4-10 membered, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 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, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; or:
R 2 and R 3 are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 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 are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ; and
Ar a is optionally substituted
7. The composition of claim 6 , wherein each R 1a is optionally substituted C 1-6 aliphatic or phenyl.
8. The composition of claim 6 , wherein R 1 is
9. The composition of claim 5 , wherein the tungsten-containing compound is a compound of formula II:
wherein:
each of R 2 and R 3 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; or:
R 2 and R 3 are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 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 are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ;
Ar a is optionally substituted
n is 0-2; and
each R8 is independently a phosphorus-containing ligand, wherein the phosphorus-containing ligand is bonded to W through a phosphorus atom.
10. The composition of claim 9 , wherein the compound of formula II has the structure of formula II-a:
wherein:
R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ;
Ar a is optionally substituted
each R 6 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R;
each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 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 are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
R 7 is optionally substituted phenyl;
n is 0-2; and
each R8 is independently a phosphorus-containing ligand, wherein the phosphorus-containing ligand is bonded to W through a phosphorus atom.
11. The composition of claim 6 , wherein R 4 is optionally substituted
12. The composition of claim 5 , wherein the tungsten-containing compound is a compound of formula III:
wherein:
each of R 2 and R 3 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; or:
R 2 and R 3 are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 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 are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each R 5′ is independently —OAr b ;
Ar b is
or an optionally substituted group selected from phenyl, a 10-14 membered bicyclic or polycyclic aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-14 membered bicyclic or polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur;
Ring B is an optionally substituted group selected from phenyl or a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;
Ring B′ is an optionally substituted group selected from phenyl, a 10-14 membered bicyclic or tricyclic aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-14 membered bicyclic or tricyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each Ring C is independently an optionally substituted group selected from phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 6-14 membered bicyclic or tricyclic 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 8-14 membered bicyclic or tricyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur;
each R x is independently R, halogen, —CN, —C(O)R, —C(O)OR, —C(O)N(R) 2 , —C(O)N(R)(OR), —OR, —OC(O)R, —OC(O)N(R) 2 , —OSi(R) 3 , —SR, —S(O)R, —S(O) 2 R, —S(O) 2 OR, —S(O) 2 N(R) 2 , —NO 2 , —N(R) 2 , —NROR, —NRC(O)R, —N(R)C(O)OR, —N(R)C(O)N(R) 2 , —N(R)S(O) 2 R, —N(R)S(O) 2 N(R) 2 , —P(R) 2 , —P(OR) 2 , —P(O)(R) 2 , —P(O)(OR) 2 , —P(O)[N(R) 2 ] 2 , or —Si(R) 3 ;
each R 5a is independently R;
each of p and t is independently 0-7;
m is 0-3;
n is 0-2; and
each R 9 is independently a neutral ligand.
13. The composition of claim 12 , wherein the tungsten-containing compound is coordinated to a Lewis acid having the structure of B(R) 3 .
14. A method for preparing a poly(dicyclopentadiene) polymer having greater than 95% syndiotacticity as determined by 13 C NMR, the method comprising:
a) providing a substrate; and
b) providing a tungsten-containing catalyst.
15. The method of claim 14 , further comprising providing a Lewis acid.
16. The method of claim 15 , wherein the Lewis acid comprises boron.
17. The polymer of claim 1 , wherein the poly(dicyclopentadiene) polymer is a hydrogenated poly(dicyclopentadiene) polymer.
18. The polymer of claim 17 , wherein the polymer is greater than 96%, greater than 97%, greater than 98%, greater than 99%, or greater than 99.5% syndiotactic as determined by 13 C NMR.
19. The polymer of claim 3 , wherein the polymer is greater than 96%, greater than 97%, greater than 98%, or greater than 99% syndiotactic as determined by 13 C NMR.
20. The polymer of claim 3 , wherein the polymer is 100% syndiotactic as determined by 13 C NMR, and the double bonds in the polymer backbone are 100% cis.