Highly Z-selective olefin metathesis
AssigneesMassachusetts Institute of Technology, The Trustees of Boston College
InventorsRichard R. Schrock, Annie J. King, Yu Zhao, Margaret M. Flook, Amir H. Hoveyda
Life of this patent
Estimating the term…
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.
Claims16
A metal complex having the structure:
- wherein:
- M is W;
- R1 is aryl, heteroaryl, alkyl, heteroalkyl, optionally substituted;
- R2 and R3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, optionally substituted;
- and
- R4 and R5 can be the same or different and are alkyl, heteroalkyl, aryl, heteroaryl, silylalkyl, or silyloxy, optionally substituted;
- one of R4 and R5 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, wherein the ligand containing oxygen bound to M is substituted —O-aryl wherein the aryl group is 1,2,3,4-tetrahydronaphthyl or naphthyl, or the ligand containing oxygen bound to M is:
- wherein R7 is aryl, heteroaryl, alkyl, or heteroalkyl, optionally substituted;
- R8 is hydrogen, —OH, halogen, alkyl, heteroalkyl, aryl, heteroaryl, acyl, acyloxy, or —OP, optionally substituted;
- or,
- together R7 and R8 are joined to form a ring, optionally substituted;
- R9 is —OH, which is deprotonated upon coordination to M;
- R19 is alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
- each R11, R12, R13, and R14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted;
- or,
- together R11 and R12 are joined to form a ring, optionally substituted;
- or
- together R13 and R14 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 R7 and R8 can be the same or different and is hydrogen, halogen, alkyl, alkoxy, aryl, acyl, or a protecting group, optionally substituted;
- R10 is alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
- each R11, R12, R13, and R14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted;
- or,
- together R11 and R12 are joined to form a ring, optionally substituted;
- or,
- together R13 and R14 are joined to form a ring, optionally substituted;
- R15 is alkyl, aryl, or a protection group, optionally substituted;
- R16 is hydrogen or an amine protecting group;
- X can be any non-interfering group;
- each Z can be the same or different and is (CH2)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.
A metal complex selected from the group consisting of M(NAr)(Pyr)(C3H6)(OHIPT), M(NAr)(CHCMe2Ph)(Pyr)(BiphenTMS), M(NAr)(CHCMe2Ph)(Me2Pyr)(Br2Bitet), wherein M=W, M(NAr)(CHCMe2Ph)(Me2Pyr)(MesBitet), W(NAr)(CHCMe2Ph)(Me2Pyr)(OPhPh4), M(NAr)(CHCMe2Ph)(Pyr)((Trip)2BitetTMS), M(NArCl)(CHCMe3)(Pyr)(BiphenTMS), M(NArCl)(CHCMe3)(Me2Pyr)(OSi(TMS)3), M(NArCl)(CHCMe3)(Me2Pyr)(OPhPh4), M(NArCl)(CHCMe3)(Me2Pyr)(HIPTO), M(NArCl)(CHCMe3)(Me2Pyr)(HIPTO), M(NArCl)(CHCMe3)(Me2Pyr)(Br2Bitet), M(NArCl)(CHCMe3)(Me2Pyr)(MesBitet), M(NArCl)(CHCMe3)(Pyr)(Mes2Bitet), M(NAd)(CHCMe2Ph)(Me2Pyr)(OSi(TMS)3), M(NAd)(CHCMe2Ph))(Me2Pyr)(HIPTO), wherein M=W, M(NAd)(CHCMe2Ph)(Me2Pyr)(MesBitet), M(NAr)(Pyr)(CHR2)(OHIPT), M(NAr′)(CHCMe2Ph)(Me2Pyr)(OSi(TMS)3), M(NAr′)(CHCMe2Ph)(Me2Pyr)(OPhPh4), M(NAr)(CHCMe2Ph)(Me2Pyr)(HIPTO), M(NAr′)(CHCMe2Ph)(Me2Pyr)(Br2Bitet), M(NAr′)(CHCMe2Ph)(Pyr)(MesBitet), M(NAr′)(CHCMe2Ph)(Me2Pyr)(MesBitet), M(NAr′)(CHCMe2Ph)(Pyr)(Mes2BitetOMe), or M(NAr′)(CHCMe2Ph)(Pyr)(Mes2Bitet), wherein M is Mo or W, Ar is 2,6-diisopropylphenyl, ArCl is 2,6-dichlorophenyl, Ar′ is 2,6-dimethyphenyl, Ad is 1-admantyl, Mes is mesityl, Me2Pyr is 2,5-dimethylpyrrolide, Pyr is pyrrolide, TBS is dimethyl-t-butylsilyl, Trip is 2,4,6-triisopropylphenyl, HIPTO is hexaisopropylterphenolate, OSi(TMS)3 is 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilan-2-olate, Biphen is 3,3′-di-tert-butyl-5,5′,6,6′-tetramethylbiphenyl-2,2′-diol, BiphenTMS is 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-2′-(trimethylsilyloxy)biphenyl-2-olate, Bitet is 5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diol, Trip2Bitet is 3,3′-bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diol, Trip2BitetTMS is 3,3′-bis(2,4,6-triisopropylphenyl)-2′-(trimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate, Br2Bitet is 3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate, MesBitet is 2′-(tert-butyldimethylsilyloxy)-3-mesityl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate, Mes2Bitet is 3,3′-dimesityl-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate, and Mes2BitetOMe is 3,3′-dimesityl-2′-methoxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate.
Dependencies are inferred from the claim text.