Z-selective ring-closing metathesis reactions

Patent metadata

Field	Value
Publication number	US-9446394-B2
Application number	US-201514641293-A
Country	US
Kind code	B2
Filing date	Mar 6, 2015
Priority date	Jun 3, 2011
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

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

First claim

What is claimed is:

1. A metal complex 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 ;
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;
each R 7 is independently optionally substituted —Ar′;
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′;

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;

wherein at least one R s is —F, and the metal complex is other than

2. The metal complex of claim 1 , wherein:
R 8 is substituted phenyl, wherein one or more substituents are —F.

3. A metal complex of formula II-c:

wherein:
M is molybdenum or tungsten;
R 8 is phenyl substituted with one to five R 9 , wherein at least one R 9 is —F;
each R 9 is independently halogen or R 1 ;
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;
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′, —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′;

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

Assignees

• Massachusetts Inst Technology
• Trustees Boston College

Inventors

• Hoveyda Amir H
• Yu Miao
• Wang Chenbo
• Schrock Richard R

Classifications

• B01J31/2265

  Carbenes or carbynes, i.e.(image) · CPC title

• C07F11/00 Primary

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title

• B01J31/2295 Primary

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• C07D493/04

  Ortho-condensed systems · CPC title