Halogen-containing metathesis catalysts and methods thereof

Patent metadata

Field	Value
Publication number	US-11020730-B2
Application number	US-201716317452-A
Country	US
Kind code	B2
Filing date	Jul 14, 2017
Priority date	Jul 15, 2016
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

The present disclosure provides compounds, compositions, and methods for preparing alkenyl halides and/or haloalkyl-substituted olefins with Z-selectivity. The methods are particularly useful for preparing alkenyl fluorides such as CF 3 -substituted olefins by means of cross-metathesis reactions using halogen-containing molybdenum and tungsten complexes.

First claim

The invention claimed is:

1. A method for performing an alkene metathesis reaction, comprising:
reacting a first species comprising a first carbon to carbon double bond with a second species comprising a second carbon to carbon double bond in the presence of a compound of formula I-a, to provide at least one product comprising a third carbon to carbon double bond, wherein:
a carbon atom of the first carbon to carbon double bond in the first species is substituted with a first substituent selected from halogen and optionally substituted C 1-6 haloalkyl; and
the third carbon to carbon double bond in the at least one product comprises a carbon atom of the first carbon to carbon double bond and a carbon atom of the second carbon to carbon double bond, wherein the carbon atom of the first carbon to carbon double bond is substituted with the first substituent;
wherein each carbon atom of the first carbon to carbon double bond in the first species is independently substituted with the first substituent;
wherein the first species is

wherein each of X and Y is independently halogen or independently optionally substituted C 1-6 haloalkyl; or
wherein

is cis-1,2-dichloroethene or cis 1,2-dibromoethene or cis-1,1,1,4,4,4-hexafluoro-2-butene; or
wherein a carbon atom of the first carbon to carbon double bond in the first species is independently substituted with an optionally substituted C 1-6 haloalkyl group, and the at least one product comprises a third carbon to carbon double bond substituted with the optionally substituted C 1-6 haloalkyl group, and wherein the optionally substituted C 1-6 haloalkyl is methyl substituted with one to three halogens, wherein the optionally substituted C 1-6 haloalkyl comprises one or more —F; or wherein the optionally substituted C 1-6 haloalkyl is methyl substituted with one to three halogens, wherein at least one halogen is —F; or wherein the optionally substituted C 1-6 haloalkyl is —CH 2 F, —CHF 2 , —CClF 2 , —CF 3 , —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —C 5 F 11 , or —C 6 F 13 ;
wherein the alkene metathesis reaction is a Z-selective cross-metathesis reaction or a Z-selective ring-opening cross metathesis reaction; and
wherein the compound of formula I-a is:

M is molybdenum;
wherein:
R 1 is adamantyl, tert-butyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 2,6-dimethylphenyl, 2,6-di-t-butylphenyl, 2,6-diisopropylphenyl, or pentafluorophenyl;
one of R 2 and R 3 is hydrogen and the other is —C(Me) 3 or is —C(Me) 2 Ph or is phenyl or 2-methoxyphenyl or 2-isopropoxyphenyl;
R 4 is 2,6-(2,6-dimethylphenyl) 2 C 6 H 3 , 2,6-(mesityl) 2 C 6 H 3 , 2,6-(2,6-diethylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triethylphenyl) 2 C 6 H 3 , 2,6-(2,6-diisopropylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triisopropylphenyl) 2 C 6 H 3 , 2,6-(2,6-di-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-tri-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,6-diphenylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triphenylphenyl) 2 C 6 H 3 , 2,6-(3,5-di-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,6-dichlorphenyl) 2 C 6 H 3 , 2,6-(2,4,6-trichlorophenyl) 2 C 6 H 3 , 2,4,6-(mesityl) 3 C 6 H 2 , 2,3,5,6-(phenyl) 4 C 6 H, or 2,3,4,5,6-(phenyl) 5 C 6 ;
R 5 is —Cl or Br;
R 6 is selected from the group consisting of an ether, a nitrile, a phosphine, a pyridine, and an amine; and
n is 0-2.

2. The method of claim 1 , wherein the method is performed in the presence of a compound selected from the group consisting of: trityl tetrakis(pentafluorophenyl)borate [(C 6 H 5 ) 3 CB(C 6 F 5 ) 4 ], sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate [Na(B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 )], tris(pentafluorophenyl)boron [B(C 6 F 5 ) 3 ], dimethylanilinium tetrakis(pentafluorophenyl) borate [PhNMe 2 HB(C 6 F 5 ) 4 ], and CuCI.

3. The method of claim 1 , wherein the compound of formula I-a is selected from:

Mo(NAd)(CHCMe 2 Ph)(OHMT)(Br)(py), Mo(NAd)(CHR)(OHMT)(Cl)(py), Mo(NAd)(CHR)(OHMT)(Br)(MeCN), Mo(NAd)(CHR)(OHMT)(Cl)(MeCN), Mo(NC 6 F 5 )(CHR)(OHMT)(Br)(py), Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(py), Mo(N-t-Bu)(CHCMe 2 Ph)(OHMT)(Cl)(MeCN), Mo(N-t-Bu)(CHCMe 2 Ph)(OHIPT)(Cl)(MeCN), Mo(N-t-Bu)(CHCMe 2 Ph)(OTBT)(Cl)(MeCN), Mo(NAd)(CHR)(OHMT)(Br), Mo(NAd)(CHR)(OHMT)(Cl)(ADNH 2 ), Mo(N-t-Bu)(CHt-Bu)(OHMT)(Cl)(MeCN), Mo(N-t-Bu)(CHt-Bu)(OHMT)(Br)(MeCN), Mo(N-t-Bu)(CHt-Bu)(OHIPT)(Cl)(MeCN), Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(PhMe 2 P), Mo(NC 6 F 5 )(CHR)(OHIPT)(Cl)(PhMe 2 P), and Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(Me 3 P),
wherein Ad is adamant-1-yl, AdNH 2 is 1-amino-adamantane, py is pyridine, Ph is phenyl, Me is methyl, R is —CMe 2 Ph, OHMT is O-2,6-(mesityl) 2 C 6 H 3 , OHIPT is O-2,6-(2,4,6-(i-Pr) 3 C 6 H 2 ) 2 C 6 H 3 , and OTBT is O-2,6-(3,5-(di-t-Bu-phenyl) 2 C 6 H 3 ).

Assignees

• Massachusetts Inst Technology
• Trustees Boston College

Inventors

• Hoveyda Amir H
• Koh Ming Joo
• Nguyen Thach T
• Schrock Richard R
• Hyvl Jakub

Classifications

• B01J2231/543

  alkene metathesis · CPC title

• C07C17/275 Primary

  of hydrocarbons and halogenated hydrocarbons · CPC title

• B01J31/2265

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

• B01J31/2208 Primary

  Oxygen, e.g. acetylacetonates · CPC title

• C07C67/333

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title