Selective olefin metathesis with cyclometalated ruthenium complexes

Patent metadata

Field	Value
Publication number	US-2016185684-A1
Application number	US-201514789848-A
Country	US
Kind code	A1
Filing date	Jul 1, 2015
Priority date	Jul 2, 2014
Publication date	Jun 30, 2016
Grant date	—

Abstract

This invention relates generally to C—H activated ruthenium olefin metathesis catalyst compounds which are stereogenic at the ruthenium center, to their preparation, and the use of such catalysts in the metathesis of olefins and olefin compounds. In particular, the invention relates to the use of C—H activated ruthenium olefin metathesis catalyst compounds in Z-selective olefin metathesis reactions, enantio-selective olefin metathesis reactions, and enantio-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

What is claimed is:

1 . An olefin metathesis catalyst complex, represented by Formula (VI),

wherein:
R 1 is C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl, C 5 -C 8 substituted cycloalkyl, C 1 -C 6 alkoxy, or halide, where the substituents are selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or halide;
R 2 is heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, where the substituents are selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or halide;
R 8 is selected from hydrogen, C 2 -C 10 alkyl, substituted C 1 -C 10 alkyl, C 5 -C 10 aryl, substituted C 5 -C 10 aryl, C 5 -C 10 heteroaryl, substituted C 5 -C 10 heteroaryl, halide (—Cl, —F, —Br, —I), hydroxyl, C 1 -C 6 alkoxy, C 5 -C 10 aryloxy, nitro (—NO 2 ), ester (—COOR 9 ), ketone (—COR 9 ), aldehyde (—COH), acyl (—COR 9 ), ester (—OCOR 9 ), carboxylic acid (—COOH), sulfonamide (—NR 9 SO 2 Ar), carbamate (—NCO 2 R 9 ), cyano (—CN), sulfoxide (—SOR 9 ), sulfonyl (—SO 2 R 9 ), sulfonic acid (—SO 3 H), fluoromethyl (—CF n ), fluroaryl (e.g., —C 6 F 5 , p-CF 3 C 6 H 4 ), where R 9 is hydrogen, methyl, C 2 -C 6 alkyl, substituted C 2 -C 6 alkyl, C 5 -C 10 aryl, or substituted C 5 -C 10 aryl, wherein n is 1, 2, or 3;
X 1 is a bidentate anionic ligand, nitrate (NO 3 − ), C 1 -C 20 alkylcarboxylate, C 6 -C 24 arylcarboxylate, C 2 -C 24 acyloxy, C 1 -C 20 alkylsulfonato, C 5 -C 24 arylsulfonato, C 1 -C 20 alkylsulfanyl, C 5 -C 24 arylsulfanyl, C 1 -C 20 alkylsulfinyl, or C 5 -C 24 arylsulfinyl;
Y is a heteroatom selected from N, O, S, and P;
R 4 , R 5 , R 6 , and R 7 are each, independently, selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, wherein any combination of R 4 , R 5 , R 6 , and R 7 can be linked to form one or more cyclic groups;
n is 1 or 2; and
Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and the olefin metathesis catalyst complex of Formula (VI) is not:

2 . The olefin metathesis catalyst complex, according to claim 1 , wherein:
R 1 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or halide; R 2 is C 2 -C 6 alkyl, substituted C 1 -C 6 alkyl, (e.g., CFH 2 , CF 2 H, CF 3 , etc.), C 5 -C 8 cycloalkyl, C 5 -C 8 substituted cycloalkyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, where the substituents are selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or halide; R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen; Y is O; Z is C 1 -C 6 alkyl; n is 1; and X 1 is NO 3 − or t-BuCO 2 .

3 . The olefin metathesis catalyst complex, according to claim 2 , wherein:
R 1 is Me, OMe or F; R 2 is MeO, iPr, Me, F, or CF 3 ; and Z is i-Pr.

4 . The olefin metathesis catalyst complex, according to claim 2 , wherein:
R 1 is Me, OMe, or F; R 2 is MeO, Me, iPr, or CF 3 ; Z is i-Pr; and X 1 is NO 3 − .

5 . The olefin metathesis catalyst complex, according to claim 2 , wherein:
R 1 is MeO, Me or F; R 2 is MeO, iPr, Me or CF 3 ; Z is i-Pr; and X 1 is t-BuCO 2 .

6 . The olefin metathesis catalyst complex, according to claim 1 , selected from:

7 . A method for performing an enantio-Z-selective cross metathesis reaction, comprising: contacting a first olefin reactant with a second olefin reactant in the presence of an enantioenriched C—H activated catalyst, under conditions effective to allow the enantio-Z-selective cross metathesis reaction to occur to form at least one cross metathesis product.

8 . The method according to claim 7 , wherein the first olefin reactant comprises two terminal olefins and the second olefin reactant comprises a di-substituted olefin.

9 . The method according to claim 8 , wherein the first olefin reactant is a diene, selected from: a 1,4-diene, a 1,5-diene and a 1,6-diene.

10 . The method according to claim 8 , wherein the second olefin reactant comprises an internal olefin or a terminal olefin.

11 . The method according to claim 7 , wherein the at least one cross-metathesis product comprises a product internal olefin.

12 . The method according to claim 11 , wherein the product internal olefin is in a Z-configuration.

13 . The method according to claim 7 , wherein the first olefin reactant and the second olefin reactant may be the same or different.

14 . The method according to claim 7 , wherein the at least one cross-metathesis product has a Z:E ratio greater than 1:1.

15 . The method according to claim 7 , wherein the at least one cross-metathesis product has a Z:E ratio greater than 1:1 in favor of the Z-isomer.

16 . The method according to claim 15 , wherein the at least one cross-metathesis product has an enantiomeric excess of greater than 50%.

17 . A method for performing an asymmetric ring closing metathesis reaction, comprising: contacting an olefin reactant comprising three terminal olefins with an enantioenriched C—H activated catalyst under conditions effective to allow the asymmetric ring closing metathesis reaction to occur to form at least one ring closing metathesis product.

18 . The method according to claim 17 , wherein the olefin reactant is a triene.

19 . The method according to claim 17 , wherein the olefin reactant is a prochiral triene.

20 . The method according to claim 17 , wherein the at least one ring closing metathesis product has an enantiomeric excess of greater than 50%.

Assignees

• California Inst Of Techn

Inventors

• Hartung Jr John
• Quigley Brendan L
• Dornan Peter K
• Grubbs Robert H

Classifications

• C07C2601/08

  the ring being saturated · CPC title

• C07C2602/08

  the other ring being five-membered, e.g. indane · CPC title

• C07C2601/14

  The ring being saturated · 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

• C07C67/343

  by increase in the number of carbon atoms · CPC title