Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts

Patent metadata

Field	Value
Publication number	US-9403854-B2
Application number	US-201314055442-A
Country	US
Kind code	B2
Filing date	Oct 16, 2013
Priority date	Mar 30, 2001
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

First claim

We claim:

1. A method for synthesizing a functionalized olefin via a cross-metathesis reaction, comprising contacting (a) a first olefinic reactant with (b) a second olefinic reactant in the presence of (c) a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the catalyst has the structure of formula (VIC)

in which:
M is Ru;
X 1 and X 2 are independently selected from the group consisting of halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate;
R 1 is hydrogen and R 2 is selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, and aryl;
L is a neutral electron donor ligand selected from the group consisting of phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, imine, carboxyl, pyridine, substituted pyridine, imidazole, and substituted imidazole;
R 3 and R 4 are aromatic, substituted aromatic, heteroaromatic, substituted heteroaromatic, alicyclic, substituted alicyclic, heteroatom-containing alicyclic, or substituted heteroatom-containing alicyclic, composed of from one to about five rings; and
R 22 and R 23 , are hydrogen, and R 22A and R 23A are selected from hydrogen, lower alkyl and phenyl, or are linked to form a cyclic group; and
wherein any two or more of X 1 , X 2 , L, R 1 , R 2 , R 3 , and R 4 can be taken together to form a chelating multidentate ligand;
wherein the first olefinic reactant has the structure of formula (VIII)

wherein:
R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and —(Z) n ,-Fn,
where n is zero or 1;
Z is selected from the group consisting of hydrocarbylene and substituted hydrocarbylene linking group; and
Fn is a functional group selected from phosphonato;
wherein the second olefinic reactant has the molecular structure R 18 R 19 C═CR 20 R 21 , wherein R 18 , R 19 , R 20 , and R 21 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl.

2. The method of claim 1 , wherein:
R 1 is hydrogen, and R 2 is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenyl, and a functional group Fn; and
L is a phosphine of the formula PR 27 R 28 R 29 , where R 27 , R 28 , and R 29 are each independently aryl or C 1 -C 10 alkyl.

3. The method of claim 2 , wherein:
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , —P(phenyl) 3 , —P(phenyl) 2 (R 7 ) and —P(phenyl)(R 7 ) 2 , in which R 7 is lower alkyl; and
R 3 and R 4 are the same and are either aromatic or C 7 -C 12 alicyclic, if aromatic, each having the structure of formula (XI)

in which R 24 , R 25 , and R 26 are each independently hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, substituted aryl, halogen, or a functional group.

4. The method of claim 3 , wherein:
X 1 and X 2 are halide;
R 2 is phenyl or —CH═C(CH 3 ) 2 ;
R 3 and R 4 are mesityl, diisopinocamphenyl, or 2,4,2′,6′-tetramethylbiphenylyl;
L is selected from the group consisting of —P(cyclohexyl) 3 and —P(cyclopentyl) 3 ; and
R 22 and R 23 are hydrogen.

5. The method of claim 1 , wherein R 5 , R 6 and R 7 are hydrogen, n is zero, and Fn is phosphonato, such that the first olefinic reactant is a vinylphosphonate having the structure of formula (XII)

wherein R 27 and R 28 are hydrocarbyl.

6. The method of claim 1 , wherein for the first olefinic reactant, R 5 , R 6 and R 7 are hydrogen, n is 1, and Fn is selected from the group consisting of phosphonato.

7. The method of claim 6 , wherein Fn is phosphonato, such that the first olefinic reactant is an allylphosphonate having the structure of formula (XIII)

wherein R 27 and R 28 are hydrocarbyl.

8. The method of claim 1 , wherein the catalyst is selected from

Assignees

• California Inst Of Techn

Inventors

• Grubbs Robert H
• Chatterjee Arnab K
• Choi Tae-Lim
• Goldberg Steven D
• Love Jennifer A
• Morgan John P
• Sanders Daniel P
• Scholl Matthias
• Toste F Dean
• Trnka Tina M

Classifications

• C07D317/24

  esterified · CPC title

• C07C29/40

  with compounds containing carbon-to-metal bonds · CPC title

• C07C67/297

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups · CPC title

• C07C69/78

  Benzoic acid esters · CPC title

• C07C25/13

  containing fluorine · CPC title