Selective olefin metathesis with cyclometalated ruthenium complexes

Patent metadata

Field	Value
Publication number	US-9676676-B2
Application number	US-201514789848-A
Country	US
Kind code	B2
Filing date	Jul 1, 2015
Priority date	Jul 2, 2014
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

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 1 -C 6 alkoxy;
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; 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;
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;
Z is i-Pr; and
X 1 is t-BuCO 2 .

6. An olefin metathesis catalyst complex, selected from:

Assignees

• California Inst Of Techn

Inventors

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

Classifications

• C07F15/0046

  Ruthenium compounds · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• B01J2231/543

  alkene metathesis · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07B2200/09

  Geometrical isomers · CPC title