Optically active bisphosphinomethane, method for producing the same, and transition metal complex and asymmetric catalyst

Patent metadata

Field	Value
Publication number	US-11498935-B2
Application number	US-202017620233-A
Country	US
Kind code	B2
Filing date	Jun 9, 2020
Priority date	Jun 24, 2019
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

There is provided a novel optically active bisphosphinomethane useful as a ligand for an asymmetric catalyst, excellent in oxidation resistance in air, and easy in handling. There is also provided a transition metal complex using the optically active bisphosphinoraethane having excellent asymmetric catalytic ability as a ligand. The optically active bisphosphinomethane is represented by the general formula (1), and the transition metal complex has the optically active bisphosphinomethane as a ligand.

(In the formula, R 1 represents an adamantyl group; R 2 represents a branched alkyl group having 3 or more carbon atoms; and * represents an asymmetric center on a phosphorus atom.)

First claim

The invention claimed is:

1. An optically active bisphosphinomethane having a solid state at 25° C. and represented by the following general formula (1):

wherein R 1 represents an adamantyl group; R 2 represents a branched alkyl group having 3 or more carbon atoms; and * represents an asymmetric center on a phosphorus atom.

2. The optically active bisphosphinomethane according to claim 1 , wherein R 2 in the general formula (1) is a tert-butyl group.

3. A method for producing an optically active bisphosphinomethane according to claim 1 , comprising:
a first step of preparing a lithiated phosphine borane made by lithiating a phosphine borane represented by the following general formula (2):

wherein R 1 represents an adamantyl group, and
preparing an optically active phosphine borane derivative represented by the following general formula (4) made by converting a hydroxyl group of an optically active hydroxymethylphosphine borane represented by the following general formula (3) to a leaving functional group:

wherein R 2 represents a branched alkyl group having 3 or more carbon atoms; and * represents an asymmetric center on a phosphorus atom,

wherein R 2 represents a branched alkyl group having 3 or more carbon atoms; A represents an activated functional group of a hydroxyl group; and * represents an asymmetric center on a phosphorus atom;
a second step of reacting the lithiated phosphine borane with the optically active phosphine borane derivative represented by the general formula (4) to obtain an optically active bisphosphinomethane borane; and
a third step of deboranating the optically active bisphosphinomethane borane.

4. A transition metal complex, comprising the optically active bisphosphinomethane according to claim 1 as a ligand.

5. An asymmetric catalyst, comprising the transition metal complex according to claim 4 .

6. A method for producing an organic compound, comprising a step of carrying out a hydrogenation asymmetric reaction using the asymmetric catalyst according to claim 5 , wherein the transition metal complex comprises a metal selected from the group consisting of rhodium, ruthenium or iridium.

Assignees

• Nippon Chemical Ind

Inventors

• Imamoto Tsuneo
• Tamura Ken
• Sano Natsuhiro

Classifications

• C07F9/5077

  from starting materials having the structure P-Metal, including R2P-M+ · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J2231/645

  of C=C or C-C triple bonds · CPC title

• C07F9/5004 Primary

  Acyclic saturated phosphines · CPC title

• C07B35/02 Primary

  Reduction · CPC title