Highly z-selective and enantioselective ring opening/cross metathesis catalyzed by a resolved stereogenic-at-ru complex

Patent metadata

Field	Value
Publication number	US-2016101414-A1
Application number	US-201414890674-A
Country	US
Kind code	A1
Filing date	May 15, 2014
Priority date	May 15, 2013
Publication date	Apr 14, 2016
Grant date	—

Abstract

This invention relates generally to enantiomerically enriched C—H activated ruthenium olefin metathesis catalyst compounds which are stereogenic at ruthenium, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in enantio- and Z-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

First claim

The claimed invention is:

1 . An enantioenriched C—H activated catalyst compound having the structure of formula (II):

wherein,
M is a Group 8 transition metal;
L 1 is a neutral electron donor ligand;
Q* is a two electron anionic donor bridging moiety linking R 3 and M;
Q is a linker selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers;
X is an atom selected from C, N, O, S, and P;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing, hydrocarbyl, and functional groups;
R 3 and R 4 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing, hydrocarbyl, and functional groups;
n is zero, 1, or 2, such that n is zero when X is O or S, n is 1 when X is N or P, and n is 2 when X is C; and

X 1 is a bidentate anionic ligand.

2 . An enantioenriched C—H activated catalyst compound, selected from

3 . A method, comprising: contacting an α-olefin with a strained olefin, in the presence of an enantioenriched C—H activated catalyst under conditions and for a time period effective to allow an asymmetric ring opening cross metathesis reaction to occur.

4 . The method of claim 3 , wherein the strained olefin is represented by the structure of formula (XIII):

wherein R 13 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (“Fn”); and J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linkage, wherein when J is substituted hydrocarbylene or substituted heteroatom-containing hydrocarbylene, the substituents may include one or more —(Z) n -Fn groups, wherein n is zero or 1.

5 . The method of claim 4 , wherein the strained olefin is a mono-unsaturated cyclic olefin reactant.

6 . The method of claim 4 , wherein the strained olefin is a bicyclic olefinic reactant or a polycyclic olefinic reactant.

7 . The method of claim 3 , wherein the α-olefin is represented by the structure of formula (XVIII):

wherein,
Y α is selected from the group comprising nil, CH 2 , O, or S; and
R α is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl and substituted heteroatom-containing hydrocarbyl wherein the substituents may be functional groups (“Fn”).

8 . The method of claim 3 , wherein the enantioenriched C—H activated catalyst has the structure of formula (II),

wherein,
M is a Group 8 transition metal;
L 1 is a neutral electron donor ligand;
Q* is a two electron anionic donor bridging moiety linking R 3 and M;
Q is a linker selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers;
X is an atom selected from C, N, O, S, and P;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing, hydrocarbyl, and functional groups;
R 3 and R 4 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing, hydrocarbyl, and functional groups;
n is zero, 1, or 2, such that n is zero when X is O or S, n is 1 when X is N or P, and n is 2 when X is C; and
X 1 is a bidentate anionic ligand.

9 . An asymmetric ring opening cross metathesis product prepared by the method of claim 3 .

10 . An asymmetric ring opening cross metathesis product of claim 9 having a Z:E ratio greater than 1:1 in favor of the Z-isomer.

11 . An asymmetric ring opening cross metathesis product of claim 10 having an enantiomeric excess of greater than 50%.

12 . A method, comprising: reacting an α-olefin with a strained olefin, in the presence of an enantioenriched C—H activated catalyst, to form an asymmetric ring opening cross metathesis product with a Z:E ratio greater than 1:1 in favor of the Z-isomer.

13 . The method of claim 12 , wherein the asymmetric ring opening cross metathesis product is produced in an enantiomeric excess of greater than 50%.

Assignees

• California Inst Of Techn

Inventors

• Hartung John
• Grubbs Robert H

Classifications

• C07D307/93

  condensed with a ring other than six-membered · CPC title

• C07C41/18

  by reactions not forming ether-oxygen bonds · CPC title

• C07C201/02

  Preparation of esters of nitric acid · CPC title

• C07C67/475

  by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules · CPC title

• C07F5/04

  Esters of boric acids · CPC title