Highly z-selective olefin metathesis

Patent metadata

Field	Value
Publication number	US-2016008802-A1
Application number	US-201514797834-A
Country	US
Kind code	A1
Filing date	Jul 13, 2015
Priority date	Sep 30, 2009
Publication date	Jan 14, 2016
Grant date	—

Abstract

The present invention relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.

First claim

What is claimed:

1 - 39 . (canceled)

40 . A metal complex having the structure:

wherein:
M is Mo or W;
R 1 is aryl, heteroaryl, alkyl, heteroalkyl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, optionally substituted; and
R 4 and R 5 can be the same or different and are alkyl, heteroalkyl, aryl, heteroaryl, silylalkyl, or silyloxy, optionally substituted;
one of R 4 and R 5 is a ligand containing oxygen bound to M, optionally substituted, and the other is a ligand containing nitrogen bound to M, optionally substituted;
the ligand containing oxygen bound to M is substituted —O-aryl wherein substituents positioned in close proximity to the metal center are sterically large groups, or the ligand containing oxygen bound to M is:

wherein R 7 is aryl, heteroaryl, alkyl, or heteroalkyl, optionally substituted;
R 8 is hydrogen, —OH, halogen, alkyl, heteroalkyl, aryl, heteroaryl, acyl, acyloxy, or —OP, optionally substituted; or,
together R 7 and R 8 are joined to form a ring, optionally substituted;
R 9 is —OH, which is deprotonated upon coordination to M;
R 10 is alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
each R 11 , R 12 , R 13 , and R 14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted; or,
together R 11 and R 12 are joined to form a ring, optionally substituted; or
together R 13 and R 14 are joined to form a ring, optionally substituted; and
P is a protecting group; or

the ligand containing oxygen bound to M is selected from

wherein each R 7 and R 8 can be the same or different and is hydrogen, halogen, alkyl, alkoxy, aryl, acyl, or a protecting group, optionally substituted;
R 10 is alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
each R 11 , R 12 , R 13 , and R 14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted; or,
together R 11 and R 12 are joined to form a ring, optionally substituted; or,
together R 13 and R 14 are joined to form a ring, optionally substituted;
R 15 is alkyl, aryl, or a protection group, optionally substituted;
R 16 is hydrogen or an amine protecting group;
X can be any non-interfering group;
each Z can be the same or different and is (CH 2 ) m , N, O, optionally substituted;
n is 0-5;
m is 1-4; and
the —OH group is deprotonated upon coordination to M;
a sterically large group is an optionally substituted group selected from tert-butyl, isopropyl, adamantyl, and naphthyl, or a substituted phenyl group.

41 . The metal complex of claim 40 , wherein the ligand containing oxygen bound to M is substituted —O-aryl, wherein the aryl group is phenyl.

42 . The metal complex of claim 40 , the ligand containing oxygen bound to M is substituted —O-aryl, wherein the aryl group is biphenyl.

43 . The metal complex of claim 40 , the ligand containing oxygen bound to M is substituted —O-aryl, wherein the aryl group is 1,2,3,4-tetrahydronaphthyl or naphthyl.

44 . The metal complex of claim 40 , wherein the ligand containing oxygen bound to M is substituted —O-aryl, and substituents positioned in close proximity to the metal center are alkylaryl.

45 . The metal complex of claim 40 , wherein the metal complex is other than W(NAr)(CHCMe 2 Ph)(Pyr)(HIPTO).

46 . The metal complex of claim 40 , wherein the ligand containing oxygen bound to M is 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-2′-(trimethylsilyloxy)biphenyl-2-olate (BiphenTMS), 2′-(tert-butyldimethylsilyloxy)-3-mesityl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate (MesBitet), 3,3′-dimesityl-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate (Mes 2 Bitet), or Mes 2 BitetOMe is 3,3′-dimesityl-2′-methoxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate (Mes 2 BitetOMe).

47 . The metal complex of claim 40 , wherein the ligand containing oxygen bound to M is

48 . The metal complex of claim 40 , the ligand containing oxygen bound to M is selected from

49 . The metal complex of claim 48 , wherein R 10 is tert-butyl, optionally substituted.

50 . The metal complex of claim 48 , wherein R 10 is substituted phenyl.

51 . The metal complex of claim 40 , wherein the nitrogen bound to M in the nitrogen-containing ligand is a ring atom of a heteroaryl group.

52 . The metal complex of claim 40 , wherein the ligand containing nitrogen bound to M is selected from the group consisting of pyrrolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, indolyl, indazolyl, carbazolyl, morpholinyl, piperidinyl, and oxazinyl, all optionally substituted.

53 . The metal complex of claim 40 , wherein the ligand containing nitrogen bound to M is pyrrolyl, optionally substituted.

54 . The metal complex of claim 40 , wherein the ligand containing nitrogen bound to M has the structure:

wherein each R 6 can be the same or different and is hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted; and
X may be present or absent and is any non-interfering group.

55 . The metal complex of claim 40 , wherein the alkylidene group is mono-substituted in that one of R 2 and R 3 is hydrogen, and the other is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted.

56 . The metal complex of claim 40 , wherein R 1 is substituted phenyl.

57 . The metal complex of claim 40 , wherein the metal complex is isolated.

58 . A metal complex selected from the group consisting of M(NAr)(Pyr)(CHR 2 )(OHIPT), M(NAr)(Pyr)(C 3 H 6 )(OHIPT), M(NAr)(CHCMe 2 Ph)(Pyr)(BiphenTMS), M(NAr)(CHCMe 2 Ph)(Me 2 Pyr)(Br 2 Bitet), M(NAr)(CHCMe 2 Ph)(Me 2 Pyr)(MesBitet), W(NAr)(CHCMe 2 Ph)(Me 2 Pyr)(OPhPh 4 ), M(NAr)(CHCMe 2 Ph)(Pyr)((Trip) 2 BitetTMS), M(NAr Cl )(CHCMe 3 )(Pyr)(BiphenTMS), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(OSi(TMS) 3 ), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(OPhPh 4 ), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(HIPTO), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(HIPTO), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(Br 2 Bitet), M(NAr Cl )(CHCMe 3 )(Me 2 Pyr)(MesBitet), M(NAr Cl )(CHCMe 3 )(Pyr)(Mes 2 Bitet), M(NAd)(Me 2 Pyr)(CHR 2 )(Br 2 Bitet), M(NAr′)(Pyr)(CHR 2 )(Mes 2 BitetOMe), M(NAd)(CHCMe 2 Ph)(Me 2 Pyr)(OSi(TMS) 3 ), M(NAd)(CHCMe 2 Ph))(Me 2 Pyr)(HIPTO), M(NAd)(CHCMe 2 Ph)(Me 2 Pyr)(MesBitet), M(NAr′)(Pyr)(CHR 2 )(OHIPT), M(NAr′)(CHCMe 2 Ph)(Me 2 Pyr)(OSi(TMS) 3 ), M(NAr′)(CHCMe 2 Ph)(Me 2 Pyr)(OPhPh 4 ), M(NAr′)(CHCMe 2 Ph)(Me 2 Pyr)(HIPTO), M(NAr′)(CHCMe 2 Ph)(Me 2 Pyr)(Br 2 Bitet), M(NAr′)(CHCMe 2 Ph)(Pyr)(MesBitet), M(NAr′)(CHCMe

Assignees

• Massachusetts Inst Technology
• Trustees Boston College

Inventors

• Schrock Richard R
• King Annie J
• Zhao Yu
• Flook Margaret M
• Hoveyda Amir H

Classifications

• B01J31/1805 Primary

  the ligands containing nitrogen · CPC title

• C07C6/04

  at a carbon-to-carbon double bond · CPC title

• B01J2540/225

  comprising perfluoroalkyl groups or moieties · CPC title

• B01J2531/64

  Molybdenum · CPC title

• B01J2531/0288

  Sterically demanding or shielding ligands · CPC title