Metal complex including tridentate aminodicarbene ligand and hydrogenation reduction method using same

Patent metadata

Field	Value
Publication number	US-9840527-B2
Application number	US-201414899424-A
Country	US
Kind code	B2
Filing date	Jun 19, 2014
Priority date	Jun 20, 2013
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

The use of a metal complex containing a ruthenium ion or an osmium ion, and a tridentate aminodicarbene ligand, the tridentate aminodicarbene ligand having one secondary amino group and two specific heterocyclic carbene groups sandwiching the amino group, enables hydrogenation reduction of carbonyl compounds, such as ketones, carboxylic acid esters, lactones, carboxylic acid amides, and lactams, and imine compounds under relatively mild conditions to produce corresponding alcohols, amines, and the like in a high yield with high catalytic efficiency. The metal complex is obtained by a method comprising steps of reacting a specific metal compound with a specific aminodicarbene precursor and subsequently reacting a specific compound. Reduction of a carbonyl compound or an imine compound in the presence of this metal complex using a hydrogen donor makes it possible to reduce the carbonyl compound or imine compound by hydrogenation.

First claim

The invention claimed is:

1. A metal complex containing a ruthenium ion or an osmium ion, and a tridentate aminodicarbene ligand,
the tridentate aminodicarbene ligand having one secondary amino group and two heterocyclic carbene groups sandwiching the amino group, the heterocyclic carbene groups being represented by Formula L 1 and/or Formula L 2 :

wherein R 1 to R 3 are identical or different and each independently represents hydrogen, halogen, hydroxyl, oxyanion (—O − ), hydroxycarbonyl, nitro, cyano, sulfo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted optionally substituted heterocyclic, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted carboxylic anhydride, optionally substituted amino, optionally substituted acyloxy, or optionally substituted sulfonyloxy, or
R 1 and R 2 , and/or R 2 and R 3 , taken together, form optionally substituted divalent hydrocarbon or optionally substituted divalent heteroatom-containing hydrocarbon; and
R 4 to R 8 are identical or different and each independently represents hydrogen, halogen, hydroxyl, oxyanion (—O − ), hydroxycarbonyl, nitro, cyano, sulfo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclic, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted carboxylic anhydride, optionally substituted amino, optionally substituted acyloxy, or optionally substituted sulfonyloxy, or
R 5 and R 6 , and/or R 7 and R 8 , taken together, form optionally substituted divalent hydrocarbon or optionally substituted divalent heteroatom-containing hydrocarbon,
wherein the tridentate aminodicarbene ligand is represented by Formula (1):

wherein Q 1 and Q 2 are identical and each represents methylene, ethylene, or propylene, and two Ls are identical or different and each represents L 1 or L 2 .

2. The metal complex according to claim 1 , wherein R 1 to R 3 are identical or different and each independently represents hydrogen, halogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclic, optionally substituted alkoxy, or optionally substituted aryloxy, or
R 1 and R 2 , and/or R 2 and R 3 , taken together, form optionally substituted alkylene, optionally substituted alkenylene, or optionally substituted oxyalkylene; and
R 4 to R 8 are identical or different and each independently represents hydrogen, halogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclic, optionally substituted alkoxy, or optionally substituted aryloxy, or
R 5 and R 6 , and/or R 7 and R 8 , taken together, form optionally substituted alkylene, optionally substituted alkenylene, or optionally substituted oxyalkylene.

3. The metal complex according to any claim 1 , wherein R 3 of Formula L 1 is optionally substituted alkyl, and R 8 of Formula L 2 is optionally substituted alkyl.

4. The metal complex according to claim 1 , wherein R 3 of Formula L 1 is optionally substituted straight-chain alkyl, and R 8 of Formula L 2 is optionally substituted straight-chain alkyl.

5. The metal complex according to claim 1 , wherein the metal complex has a composition represented by Formula (2) or (3):
[M(A)Y 1 Y 2 Z 1 ]  (2)

[M(A)Y 1 Z 1 Z 2 ]Y 2   (3)

wherein
M is a ruthenium ion or an osmium ion,
A is a tridentate aminodicarbene ligand,
Y 1 and Y 2 are identical or different and each represents a monovalent anionic ligand, and
Z 1 and Z 2 are identical or different and each represents a monodentate ligand.

6. The metal complex according to claim 5 , wherein the monodentate ligand represents CO; PR 1a R 1b R 1c , wherein R 1a , R 1b , and R 1c are identical or different and each represents optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, or optionally substituted heterocyclic; P(OR 2a )(OR 2b )(OR 2c ), wherein R 2a , R 2b , and R 2c are identical or different and each represents optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, or optionally substituted heterocyclic; SR 3a R 3b , wherein R 3a and R 3b are identical or different and each represents optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, or optionally substituted heterocyclic; a nitrile compound; an isonitrile compound; N 2 ; PF 3 ; CS; tetrahydrothiophene; or C 1-5 alkene.

7. The metal complex according to claim 5 , wherein at least one of Y 1 and Y 2 of Formulae (2) and (3) is a halogen ion.

8. The metal complex according to claim 1 , for use as a reduction catalyst for a reaction of reducing a carbonyl compound or an imine compound using a hydrogen donor.

9. A method for producing the metal complex according to claim 1 ,
the method comprising steps of reacting a metal compound (II) with an aminodicarbene precursor (I), and subsequently reacting the resulting product with a compound (III),
wherein the aminodicarbene precursor (I) has one secondary amino group and two heterocyclic groups sandwiching the amino group, the two heterocyclic groups being represented by Formula L 1′ or L 2′ :

wherein R 1 to R 3 are identical or different and each independently represents hydrogen, halogen, hydroxyl, oxyanion (—O − ), hydroxycarbonyl, nitro, cyano, sulfo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclic, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted carboxylic anhydride, optionally substituted amino, optionally substituted acyloxy, or optionally substituted sulfonyloxy, or
R 1 and R 2 , and/or R 2 and R 3 , taken together, form optionally substituted divalent hydrocarbon or optionally substituted divalent heteroatom-containing hydrocarbon;
R 4 to R 8 are identical or different and each independently represents hydrogen, halogen, hydroxyl, oxyanion (—O − ), hydroxycarbonyl, nitro, cyano, sulfo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclic, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted carboxylic anhydride, optionally substituted amino, optionally substituted acyloxy, or optionally substituted sulfonyloxy, or
R 5 and R 6 , and/or R 7 and R 8 , taken together, form optionally substituted divalent hydrocarbon or optionally substituted divalent heteroatom-containing hydrocarbon;
Y 3 represents an anionic ligand; and
Y 4 represents an anionic ligand; and
wherein the metal compound (II) contains a cobalt ion, a nickel ion, a copper ion, a rhodium ion, a palladium ion, or a silver ion, and
wherein the compound (III) is represented by Formula (4):
MY 1 Y 2 Z n   (4)

wherein M represents a ruthenium ion or an osmium ion, Y 1 and Y 2 are identical or different and each represents a monovalent anionic ligand, Z is identical or different and each represen

Assignees

• Kuraray Co

Inventors

• Murata Yusuke
• Torihara Masahiro

Classifications

• B01J2231/643

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

• C07B31/00

  Reduction in general · CPC title

• C07C33/22

  Benzylalcohol; phenethyl alcohol · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title