Ruthenium complex, method for producing same, and use of same

Patent metadata

Field	Value
Publication number	US-10059729-B2
Application number	US-201515306671-A
Country	US
Kind code	B2
Filing date	Apr 24, 2015
Priority date	Apr 25, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

The present invention provides a novel ruthenium complex that is easy to produce and handle and that can be supplied relatively inexpensively, a method for producing this ruthenium complex, a method for producing alcohols and the like using this ruthenium complex as a catalyst, a method for producing carbonyl compounds using this ruthenium complex as a catalyst, and a method for producing N-alkylamine compounds using this ruthenium complex as a catalyst. The present invention pertains to a ruthenium complex represented by general formula (1) RuX 1 X 2 (PNP) (NHC) m (Solv) n (1) (in general formula (1), X 1 and X 2 each independently represent a monovalent anionic monodentate ligand; PNP represents a tridentate aminodiphosphine ligand, NHC represents an N-heterocyclic carbene derived from a nitrogen-containing heterocyclic ring, and Solv represents a coordinating solvent; and m represents an integer from 1 to 3, n represents an integer from 0 to 2, and 1≤m+n≤3.), a method for producing the same, a catalyst including the same, and methods for producing various organic compounds using this catalyst.

First claim

The invention claimed is:

1. A ruthenium complex represented by the following general formula (1):
RuX 1 X 2 (PNP)(NHC) m (Solv) n   (1)

(in the general formula (1), X 1 and X 2 each independently represent a monovalent anionic monodentate ligand; PNP represents a tridentate ligand represented by the following general formula (2):

(in the general formula (2), R 1 , R 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group, and among these groups, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group and a heterocyclic group may have substituent(s); R 1 and R 2 , and R 1 ′ and R 2 ′ each independently may bind to each other to form a ring together with the adjacent phosphorus atom; Q 1 and Q 2 each independently represent an optionally substituted alkanediyl group or an optionally substituted aralkylene group), NHC represents an N-heterocyclic carbene derived from a nitrogen-containing heterocyclic ring, and Solv represents a coordinating solvent; m represents an integer from 1 to 3, n represents an integer from 0 to 2, and 1≤m+n≤3).

2. The ruthenium complex according to claim 1 , wherein the PNP is a tridentate ligand represented by the following general formula (3):

(in the general formula (3), R 1 , R 2 , R 1 ′ and R 2 ′ represent the groups having the same definition as in the general formula (2); R 7 , R 7 ′, R 8 , R 8 ′, R 9 , R 9 ′, R 10 and R 10 ′ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group, and among these groups, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group and a heterocyclic group may have substituent(s); R 7 , and R 8 or R 9 or R 10 , R 7 ′, and R 8 ′ or R 9 ′ or R 10 ′, R 8 , and R 9 or R 10 , R 8 ′, and R 9 ′ or R 10 ′, R 9 , and R 10 or R 9 ′ or R 10 ′, R 9 ′, and R 10 or R 10 ′ and R 10 and R 10 ′ each independently may bind to each other to form a ring together with the adjacent carbon atom(s)).

3. The ruthenium complex according to claim 2 , wherein the PNP is a tridentate ligand represented by the following general formula (4):

(in the general formula (4), R 1 , R 2 , R 1 ′ and R 2 ′ represent the groups having the same definition as in general formula (2)).

4. The ruthenium complex according to claim 3 , wherein R 1 , R 2 , R 1 ′ and R 2 ′ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group.

5. The ruthenium complex according to claim 4 , wherein NHC is any one of N-heterocyclic carbene selected from the group consisting of imidazole-ylidenes, dihydroimidazole-ylidenes, thiazole-ylidenes, dihydropyrimidine-ylidenes, hexahydro-1,3-diazepine-ylidenes, dihydrothiazole-ylidenes, oxazole-ylidenes, dihydrooxazole-ylidenes, tetrahydropyrimidine-ylidenes, pyrimidine-ylidenes and triazole-ylidenes.

6. The ruthenium complex according to claim 5 , wherein the NHC is imidazole-2-ylidenes or dihydroimidazole-2-ylidenes represented by the following general formula (5) or (6):

(in the general formulas (5) and (6), R 3 , R 3 ′, R 5 and R 5 ′ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group, and these alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group and heterocyclic group may have substituent(s); R 4 , R 4 ′, R 6 and R 6 ′ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group, and among these groups, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group and a heterocyclic group may have substituent(s); R 3 and R 3 ′, R 3 and R 4 , R 4 and R 4 ′ and R 4 ′ and R 3 ′ each independently may bind to each other to form a ring together with the adjacent atoms; R 5 and R 5 ′, R 5 and R 6 , R 6 and R 6 ′ and R 6 ′ and R 5 ′ each independently may bind to each other to form a ring together with the adjacent atoms).

7. The ruthenium complex according to claim 6 , wherein R 3 , R 3 ′, R 5 and R 5 ′ each independently represent an optionally substituted alkyl group or an optionally substituted aryl group, and R 4 , R 4 ′, R 6 and R 6 ′ each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group.

8. The ruthenium complex according to claim 1 , wherein the PNP and/or NHC is an optically active form.

9. A method for producing the ruthenium complex represented by the following general formula (1):
RuX 1 X 2 (PNP)(NHC) m (Solv) n   (1)

(in the general formula (1), X 1 , X 2 , PNP, NHC, Solv, m and n
are the same as those defined in claim 1 ), comprising:
a ruthenium complex represented by the following general formula (7):
[RuX 1 X 2 (PNP)] q   (7)

(in the general formula (7), X 1 and X 2 each independently represent a monovalent anionic monodentate ligand, PNP represents a tridentate ligand represented by the general formula (2), (3) or (4) or an optically active form thereof, and q represents an integer from 1 to 2) is reacted with NHC (NHC represents an N-heterocyclic carbene derived from nitrogen-containing heterocyclic ring or an optically active form thereof) or an NHC equivalent,
wherein the general formula (2) is:

(in the general formula (2), R 1 , R 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group, and among these groups, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group and a heterocyclic group may have substituent(s); R 1 and R 2 , and R 1 ′ and R 2 ′ each independently may bind to each other to form a ring together with the adjacent phosphorus atom; Q 1 and Q 2 each independently represent an optionally substituted alkanediyl group or an optionally substituted aralkylene group), NHC represents an N-heterocyclic carbene derived from a nitrogen-containing heterocyclic ring, and Solv represents a coordinating solvent; m represents an integer from 1 to 3, n represents an integer from 0 to 2, and 1≤m+n≤3)

wherein the general formula (3) is

(in the general formula (3), R 1 , R 2 , R 1 ′ and R 2 ′ represent the groups having the same definition as in the general formula (2); R 7

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Ogata Osamu
• Nara Hideki
• Nakayama Yuji

Classifications

• B01J2531/821

  Ruthenium · CPC title

• B01J2531/0216

  Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp · CPC title

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title

• B01J2231/643

  of R2C=O or R2C=NR (R= C, H) · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title