Catalysts for efficient Z-selective metathesis

Patent metadata

Field	Value
Publication number	US-9938253-B2
Application number	US-201414303523-A
Country	US
Kind code	B2
Filing date	Jun 12, 2014
Priority date	Jun 12, 2013
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, provided compounds promote highly efficient and highly Z-selective metathesis. In some embodiments, provided compounds and methods are particularly useful for producing allyl alcohols. In some embodiments, provided compounds have the structure of formula I. In some embodiments, provided compounds comprise ruthenium, and a ligand bonded to ruthenium through a sulfur atom.

First claim

The invention claimed is:

1. A compound, wherein the compound has the structure of formula I-c:

wherein:
each of R 6 and R 7 is independently R, —CN, halogen, —OR, —OC(O)R, —OSi(R) 3 , —SR, —S(O)R, —S(O) 2 R, —NO 2 , —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, —SeR, —Si(R) 3 , or:
R 6 and R 7 are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

or wherein the compound has the structure of formula I-d:

or wherein the compound has the structure of formula I-e:

or wherein the compound has the structure of formula I-f:

wherein
R 1 is a nitrogen-containing heterocyclic carbene;
r is 1;
X and Y is —S—;
Ring A is an optionally substituted ring selected from 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 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each R x is independently halogen, R, —CN, —C(O)N(R′) 2 , —C(O)R, —C(O)OR, —OR, —OC(O)R, —OC(O)OR, —OC(O)N(R′) 2 , —OSi(R) 3 , —N(R′) 2 , —N(R′) 3 + , —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, —NO 2 , —Si(R) 3 , —P(R) 2 , —P(O)(R) 2 , —P(O)(OR) 2 , —SR, —SC(O)R, —S(O)R, —SO 2 R, —SO 3 R, —SO 2 N(R′) 2 , or —SeR;
each R′ is independently R, —C(O)R, —C(O)N(R) 2 , —C(O)OR, —SO 2 R, —SO 2 N(R) 2 , —P(O)(OR) 2 , or —OR; and
each R is independently hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic, 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 are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
m is 0-6;
R 2 is R x ;
R 3 is hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and
Z is —O— or —S—.

2. The compound of claim 1 , wherein Z is —O—.

3. The compound of claim 1 , wherein the compound is selected from:

4. The compound of claim 1 , wherein the compound is dimerized or polymerized.

5. The compound of claim 1 , wherein the compound is linked to a tag or a solid support.

6. A method for performing a metathesis reaction, comprising providing a compound of claim 1 .

7. The compound of claim 1 , wherein one R x is —NO 2 .

8. The compound of claim 1 , wherein

9. The compound of claim 1 , wherein one R x is —SO 2 N(R′) 2 , —SO 2 R, —S(O)R, —C(O)R, —C(O)N(R′) 2 , or —NR′SO 2 R.

10. The compound of claim 1 , wherein one R x is —SO 2 N(R′) 2 .

11. The compound of claim 1 , wherein

12. The compound of claim 1 , wherein one R x is —NR′C(O)N(R′) 2 .

13. The compound of claim 1 , wherein one R x is —NHC(O)R.

14. The compound of claim 1 , wherein one R x is —NHC(O)C 6 F 5 , —NHC(O)CF 3 , —NHC(O)C(O)OEt, —NHC(O)Ot—Bu, —NHC(O)Oi—Bu, or —NHC(O)C 15 H 31 .

15. The compound of claim 1 , wherein the compound has the structure of formula I-g:

16. A compound selected from:

Assignees

• Trustees Boston College

Inventors

• Hoveyda Amir H
• Khan R Kashif M
• Torker Sebastian
• Koh Ming Joo

Classifications

• C07F7/0818

  Chemistry & Metallurgy · mapped topic

• C07C45/68

  by increase in the number of carbon atoms · CPC title

• C07C235/30

  the carbon skeleton being unsaturated and containing rings other than six-membered aromatic rings · CPC title

• C07C33/38

  Alcohols containing six-membered aromatic rings and other rings and having unsaturation outside the aromatic rings · CPC title

• B01J31/226

  Sulfur, e.g. thiocarbamates · CPC title