Ruthenium complexes comprising an asymmetrical unsaturated N-heterocyclic diaminocarbene

Patent metadata

Field	Value
Publication number	US-9776178-B2
Application number	US-201314651243-A
Country	US
Kind code	B2
Filing date	Dec 11, 2013
Priority date	Dec 12, 2012
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

The invention relates to a ruthenium alkylidene complex comprising a 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligand, the cycloalkyl group of said 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligand being a cyclic secondary aliphatic alkyl.

First claim

The invention claimed is:

1. Alkylidene ruthenium complex comprising a 1-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand, characterized in that the cycloalkyl group of said 1-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand is a cyclic secondary aliphatic alkyl.

2. Alkylidene ruthenium complex according to claim 1 , in which said complex is of general formula selected from the group consisting of formula 1,

in which
R1 is an aromatic group,
R2 is a cyclic secondary aliphatic alkyl group,
R3 and R4 are selected independently of one another from the group consisting of a hydrogen atom, a halide and an alkyl group,
X 1 and X 2 are anionic ligands,
L is an uncharged ligand, and
a, b, c, d, e and f are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group;
of formula 2:

in which
R1 is an aromatic group,
R2 is a cyclic secondary aliphatic alkyl group,
R3 and R4 are selected independently of one another from the group consisting of a hydrogen atom, a halide and an alkyl group,
X 1 and X 2 are anionic ligands, and
a, b, c, d, e and f are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group;
of formula 3:

in which
R1 is an aromatic group,
R2 is a cyclic secondary aliphatic alkyl group,
R3 and R4 are selected independently of one another from the group consisting of a hydrogen atom, a halide and an alkyl group,
X 1 and X 2 are anionic ligands, and
a, b, c, d, e, f and g are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group;
and of formula 4:

in which
R1 is an aromatic group,
R2 is a cyclic secondary aliphatic alkyl group,
R3 and R4 are selected independently of one another from the group consisting of a hydrogen atom, a halide and an alkyl group,
a, b, c, d, e and f are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group,
X 1 is an anionic ligand, and
A − is an anion.

3. Alkylidene ruthenium complex according to claim 2 , in which R1 is selected from the group consisting of 2,4,6-trimethylphenyl, 3,5-dinitrophenyl, 2,4,6-tris(trifluoromethyl)phenyl, 2,4,6-trichlorophenyl, and hexafluorophenyl.

4. Alkylidene ruthenium complex according to claim 2 , in which R2 is selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and cyclopentadecyl.

5. Alkylidene ruthenium complex according to claim 2 , in which R3 and R4 are each a hydrogen atom.

6. A method of catalysing an olefin metathesis reaction, the method comprising adding the alkylidene ruthenium complex according to claim 1 to a reaction mixture.

7. Method of preparing an alkylidene ruthenium complex comprising the following steps:
a. forming a first reaction mixture by contacting an imidazolium salt of formula 1S:

in which
R1 is an aromatic group,
R2 is selected from a cyclic secondary aliphatic alkyl group and a heteroalkyl group,
R3 and R4 are selected independently of one another from the group consisting of a hydrogen atom, a halide and an alkyl group, and
A − is an anion,
with a strong base, in a solvent, under inert atmosphere, at room temperature, for at least 30 minutes;
b. adding a ruthenium complex precursor to the reaction mixture formed in step a., and then heating at a temperature of at least 40° C. for at least 2 hours;
c. isolating an alkylidene ruthenium complex.

8. Method according to claim 7 , in which step b. is carried out at a temperature of about 80° C.

9. Method according to claim 7 , in which the ruthenium complex precursor added in step b. is of formula 1P:

in which,
X 1 and X 2 are anionic ligands,
L 1 and L 2 are uncharged ligands, preferably tricyclohexylphosphine, and
a, b, c, d, e and f are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group.

10. Method according to claim 7 , further comprising the step of:
d. forming a second reaction mixture by contacting the alkylidene ruthenium complex isolated in step c. with a styrenyl ether.

11. Method according to claim 7 , in which step b. is carried out for at least 3 hours and in which said ruthenium precursor complex is of the so-called first-generation Hoveyda-Grubbs type.

12. Method according to claim 10 , in which said styrenyl ether is of formula 4H:

in which a, b, c, d, e, f, g, i and h are selected independently of one another from the group consisting of a hydrogen atom, an alkyl group and a heteroalkyl group.

Assignees

• Ecole Nat Superieure De Chimie De Rennes
• Centre Nat Rech Scient

Inventors

• Mauduit Marc
• Rouen Mathieu

Classifications

• B01J2231/543

  alkene metathesis · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J31/2278

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

• C07F15/0046

  Ruthenium compounds · CPC title

• B01J31/2273 Primary

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title