IP Library › Granted Patent US 9,073,801

Granted Patent B2

US 9,073,801 · App. 13/487,067 · Granted Jul 7, 2015

Patent

Inventors: Amir H. Hoveyda (Lincoln, MA); Miao Yu (West Roxbury, MA); Chenbo Wang (Chestnut Hill, MA); Richard R. Schrock (Winchester, MA)

Assignees: Massachusetts Institute of Technology; Trustees of Boston College

C07B37/10 C07D313/00 C07D225/02 C07F11/00 C07D417/06 C07D245/02 C07D267/00 C07D491/18 C07D491/22

View Patent ↗

Loading inventors, assignments & file history…

Monitor This Case

Get email alerts when status or documents change.

Order Certified Copies

Most orders are placed with the USPTO same day — all within 24 business hours.

Order via The Patent Place →

Pre-filled with this patent's details

Quick Facts

Patent No.: US 9,073,801
App. No.: 13/487,067
Granted: Jul 7, 2015
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

The present invention relates generally to olefin metathesis. In some embodiments, the present invention provides methods for Z-selective ring-closing metathesis.

Claims (161)

1. A method comprising reacting a suitable diene with a stereogenic-at-metal catalyst or metal complex to form a compound of formula I:

wherein the double bond depicted therein is in the cis configuration, and wherein:

Ring A is an optionally substituted 8-30 membered saturated or partially unsaturated ring wherein 0-6 methylene units of Ring A are optionally and independently replaced by —O—, —N(R)—, —S—, —C(O)—, —OC(O)—, —C(O)O—, —OC(O)O—, —S(O)—, or —S(O) 2 —, —OSO 2 O—, —N(R)C(O)—, —C(O)N(R)—, —N(R)C(O)O—, —OC(O)NR—, —N(R)C(O)NR—, or —Cy 1 —, wherein:

each —Cy 1 — is independently:

a bivalent optionally substituted monocyclic ring independently selected from phenylene, a 3-8 membered saturated or partially unsaturated carbocyclylene, a 5-6 membered heteroarylene having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 3-8 membered saturated or partially unsaturated heterocyclylene having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or

a bivalent optionally substituted bicyclic ring independently selected from an 8-10 membered arylene, a 7-10 membered saturated or partially unsaturated carbocyclylene, an 8-10 membered heteroarylene having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7-10 membered saturated or partially unsaturated heterocyclylene having 1-5 heteroatoms selected from nitrogen, oxygen, or sulfur; or

a bivalent optionally substituted tricyclic ring independently selected from 14 membered arylene, a 9-20 membered saturated or partially unsaturated carbocyclylene, a 9-14 membered heteroarylene having 1-8 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 9-20 membered saturated or partially unsaturated heterocyclylene having 1-8 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or

a bivalent optionally substituted tetracyclic ring independently selected from a 16-18 membered arylene, an 11-30 membered saturated or partially unsaturated carbocyclylene, a 15-18 membered heteroarylene having 1-8 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 11-30 membered saturated or partially unsaturated heterocyclylene having 1-12 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

n is 0-20;

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 4-7 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, wherein:

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; or

two R groups on the same carbon atom are optionally taken together with their intervening atoms to form an optionally substituted 3-8 membered saturated or partially unsaturated spirocycle ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or

two R groups on adjacent atoms are optionally taken together with their intervening atoms form an optionally substituted 3-8 membered, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

each R A is independently selected from —R, —QR, —OR, a suitably protected hydroxyl group, —SR, a suitably protected thiol group, —S(O)R, —SO 2 R, —OSO 2 R, —N(R) 2 , a suitably protected amino group, —N(R)C(O)R, —N(R)C(O)C(O)R, —N(R)C(O)N(R) 2 , —N(R)C(O)OR, —C(O)OR, —OC(O)R, —C(O)N(R) 2 , or —OC(O)N(R) 2 , wherein:

two R A on the same carbon atom are optionally taken together to form an oxo moiety, an oxime, an optionally substituted hydrazone, an optionally substituted imine, an optionally substituted C 2-6 alkylidene, or an optionally substituted 3-8 membered saturated or partially unsaturated spirocycle having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or:

two R A on adjacent atoms are optionally taken together to form an optionally substituted 3-8 membered, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

each Q is independently an optionally substituted bivalent C 1-10 hydrocarbon chain wherein one, two, or three methylene units of Q are optionally and independently replaced by —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —S(O) 2 —, —OSO 2 O—, —N(R)C(O)—, —C(O)N(R)—, —N(R)C(O)O—, —OC(O)NR—, —N(R)C(O)NR—, or —Cy 2 —;

each —Cy 2 — is independently a bivalent optionally substituted ring selected from phenylene, a 3-8 membered saturated or partially unsaturated monocyclic carbocyclylene, a 5-6 membered monocyclic heteroarylene having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-8 membered saturated or unsaturated monocyclic heterocyclylene having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an 8-10 membered bicyclic arylene, a 7-10 membered saturated or partially unsaturated bicyclic carbocyclylene, an 8-10 membered bicyclic heteroarylene having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7-10 membered saturated or partially unsaturated bicyclic heterocyclylene having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and

wherein the catalyst or metal complex is of formula II-a:

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 4-7 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′, provided that R 2 and R 3 are not simultaneously hydrogen;

R 4 is an optionally substituted group selected from —Ar, 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 4-7 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;

Ar is of the following formula:

wherein:

m is 0-3;

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;

p and q are independently 0-6;

each of Ring C and Ring D is independently optionally substituted groups selected from 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 4-7 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 R x , R y , and R z is independently halogen, —OR′, —N(R′) 2 , —NR′C(O)R′, —NR′C(O)OR′, —NR′C(O)N(R′) 2 , —NR′SO 2 R′, —NR′SO 2 N(R′) 2 , —NR′OR′, or 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;

R 5 is halogen, —OR 6 , —N(R′) 2 , —NR′C(O)R′, —NR′C(O)OR′, —NR′C(O)N(R′) 2 , —NR′SO 2 R′, —NR′SO 2 N(R′) 2 , or —NR′OR′, or an optionally substituted group selected from a 5-6 membered monocyclic heteroaryl ring having at least one nitrogen and 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having at least one nitrogen and 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

R 6 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 4-7 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; 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 4-7 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, wherein:

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;

or wherein the catalyst or metal complex is of formula II-b:

wherein:

M is molybdenum or tungsten;

R 2′ and R 3′ are taken together with their intervening metal atom 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;

Ar is of the following formula:

wherein:

m is 0-3;

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;

each of Ring C and Ring D is independently optionally substituted groups selected from phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic rind, 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 4-7 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;

p and q are independently 0-6;

each R x , R y , and R z is independently halogen, —OR 6 , —N(R′) 2 , —NR′C(O)R′, —NR′C(O)OR′, —NR′C(O)N(R′) 2 , —NR′SO 2 R′, —NR′SO 2 N(R′) 2 , —NR′OR′, or 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;

2. The method according to claim 1 , wherein the metal complex is of formula II-a.

3. The method according to claim 1 , wherein the catalyst metal complex is of formula II-b.

4. A method comprising reacting a suitable diene with a catalyst or metal complex to form a compound of formula I-a:

wherein the double bond depicted therein is in the Z configuration, and wherein:

each —Cy 1 — is independently:

n is 0-20;

R B is —R, —QR, —OR, a suitably protected hydroxyl group, —SR, a suitably protected thiol group, —S(O)R, —SO 2 R, —OSO 2 R, —N(R) 2 , a suitably protected amino group, —N(R)C(O)R, —N(R)C(O)C(O)R, —N(R)C(O)N(R) 2 , —N(R)C(O)OR, —C(O)OR, —OC(O)R, —C(O)N(R) 2 , or —OC(O)N(R) 2 ;

wherein the catalyst or metal complex is of formula II-a:

wherein:

M is molybdenum or tungsten;

Ar is of the following formula:

wherein:

m is 0-3;

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;

p and q are independently 0-6;

R 5 is —N(R′) 2 , —NR′C(O)R′, —NR′C(O)OR′, —NR′C(O)N(R′) 2 , —NR′SO 2 R′, —NR′SO 2 n(R′) 2 , or —NR′OR′, or an optionally substituted group selected from a 5-6 membered monocyclic heteroaryl ring having at least one nitrogen and 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having at least one nitrogen and 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein R 5 is coordinated to M via a nitrogen;

or wherein the catalyst or metal complex is of formula II-b:

wherein:

M is molybdenum or tungsten;

Ar is of the following formula:

wherein:

m is 0-3;

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;

p and q are independently 0-6;

or wherein the catalyst or metal complex is of formula II-c:

wherein:

M is molybdenum or tungsten;

R 8 is R 1 , or phenyl optionally substituted with one to five R 9 ;

each R 9 is independently halogen or R 1;

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′, provided that R 2 and R 3 are not simultaneously hydrogen;

each R 7 is independently an optionally substituted group selected from —Ar′, 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 4-7 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; and two R 7 are optionally taken together with the oxygen atoms to which they are attached to form a bidentate ligand;

Ar′ is of the following formula:

wherein:

t is 0-4;

p is 0-6;

each Ring B′ and Ring C′ is independently an optionally substituted group selected from 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 4-7 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; and

each R s is independently halogen, R′, —OR′, —SR′, —S(O)R′, —S(O) 2 R′, —OSi(R′) 3 , —N(R′) 2 , —NR′C(O)R′, —NR′C(O)OR′, —NR′C(O)N(R′) 2 , —NR′SO 2 R′, —NR′SO 2 N(R′) 2 , or —NR′OR′;

and wherein the catalyst or metal complex is other than Mo(CHG)(N( 2 , 6 -( i -Pr) 2 C 6 H 3 ))(OCMe(CF 3 ) 2 ) 2 , wherein G is — t Bu or CMe 2 Ph

wherein the catalyst or metal complex is other than Mo(CHG)(N(2,6-(i-Pr) 2 C 6 H 3 ))(OCMe(CF 3 ) 2 ) 2 , wherein G is —tBu or —CMe 2 Ph, and

5. The method of claim 4 , wherein the catalyst or metal complex is of formula II-a.

6. The method of claim 4 , wherein the catalyst or metal complex is of formula II-b.

7. The method of claim 4 , wherein the catalyst or metal complex is of formula II-c.

8. The method of claim 2 , wherein R 5 is optionally substituted

9. The method of claim 8 , wherein:

R 4 is —Ar;

Ar is

and

each of R y and R z is independently optionally substituted C 1-20 aliphatic.

10. The method of claim 8 , wherein —OR 4 is an optionally substituted group selected from:

wherein each represents the point of attachment to the metal, M.

11. The method of claim 3 , wherein R 2′ and R 3′ are taken together with the intervening metal atom to form metallacyclobutane.

12. The method of claim 11 , wherein R 5 is optionally substituted

13. The method of claim 12 , wherein:

R 4 is —Ar;

Ar is

and

each of R y and R z is independently optionally substituted C 1-20 aliphatic.

14. The method of claim 1 , wherein the stereogenic-at-metal catalyst or metal complex is used in an amount of between about 0.01 mol % to about 10 mol % of catalyst relative to the suitable diene.

15. The method of claim 1 , wherein Ring A is an optionally substituted 9-30 membered saturated or partially unsaturated ring wherein 0-6 methylene units of Ring A are optionally and independently replaced by —O—, —N(R)—, —S—, —C(O)—, —OC(O)—, —C(O)O—, —OC(O)O—, —S(O)—, or —S(O) 2 —, —OSO 2 O—, —N(R)C(O)—, —C(O)N(R)—, —N(R)C(O)O—, —OC(O)NR—, —N(R)C(O)NR—, or —Cy 1 —.

16. The method of claim 15 , wherein Ring A is an optionally substituted 12-18 membered saturated or partially unsaturated ring wherein 0-6 methylene units of Ring A are optionally and independently replaced by —O—, —N(R)—, —S—, —C(O)—, —OC(O)—, —C(O)O—, —OC(O)O—, —S(O)—, or —S(O) 2 —, —OSO 2 O—, —N(R)C(O)—, —C(O)N(R)—, —N(R)C(O)O—, —OC(O)NR—, —N(R)C(O)NR—, or —Cy 1 —.

17. The method of claim 7 , wherein:

each R 7 is independently optionally substituted —Ar′, wherein one or more substituents are —F.

18. The method of claim 7 , wherein at least one —OR 7 is an optionally substituted group selected from:

wherein:

each represents the point of attachment to the metal M; and

one or more R s are —F.

19. The method of claim 18 , wherein R 8 is phenyl substituted with one to five R 9 , wherein each R 9 is independently halogen or —CF 3 .

20. The method of claim 19 , wherein R 8 is

21. The method of claim 7 , wherein R 8 is optionally substituted phenyl, wherein at least one substituent is —F.

22. The method of claim 21 , wherein R 8 is

23. The method of claim 5 , wherein R B is hydrogen.

24. The method of claim 6 , wherein R B is hydrogen.

25. The method of claim 7 , wherein R B is not hydrogen.

26. The method of claim 25 , wherein each R 7 is independently an optionally substituted group selected from —Ar′, phenyl, an 8-10 membered bicyclic 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, and each —OR′ is independently a monodentate ligand.

27. The method of claim 4 , wherein reacting a suitable diene with a catalyst or metal complex forms a compound of formula I-a in a Z:E ratio greater than 2:1.

Assignments (2)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 28, 2012

From: HOVEYDA, AMIR H.; YU, MIAO; WANG, CHENBO

To: TRUSTEES OF BOSTON COLLEGE

Reel/Frame 028862/0063 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 9, 2012

From: SCHROCK, RICHARD R.

To: MASSACHUSETTS INSTITUTE OF TECHNOLOGY

Reel/Frame 028759/0804 →

Continuity (3)

Provisional Application 61492996 · Jun 3, 2011

Provisional Application 61598307 · Feb 13, 2012

Related Publication 20120323000A1 · Dec 20, 2012