N-(phosphinoalkyl)-N-(thioalkyl)amine derivative, method for producing same, and metal complex thereof

Patent metadata

Field	Value
Publication number	US-10072033-B2
Application number	US-201515502813-A
Country	US
Kind code	B2
Filing date	Aug 26, 2015
Priority date	Aug 26, 2014
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The purpose of the present invention is to provide: a ligand that is useful in a catalytic organic synthetic reaction; a method for producing said ligand; and a metal complex that is useful as a catalyst in an organic synthetic reaction. The present invention provides a compound represented by general formula (1 A ), a method for producing said compound, and a metal complex including said compound as a ligand. (In the formula, H, N, P, S, L, R 1 , R 2 , R 3 , Q 1 , and Q 2 have the meaning as defined in the Description.)

First claim

The invention claimed is:

1. A compound of the following formula (1 A ):

wherein H is a hydrogen atom, N is a nitrogen atom, P is a phosphorus atom, and S is a sulfur atom; L is lone pair electrons or boron trihydride; R 1 , R 2 , and R 3 each independently are a group selected from the group consisting of alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, and optionally substituted aralkyl groups; R 1 and R 2 may be bonded to each other to form an optionally substituted ring; and
each of Q 1 and Q 2 is a 1,2-ethanediyl group.

2. The compound according to claim 1 , wherein the compound is an optically active compound.

3. A Bronsted acid salt of the compound according to claim 1 , wherein
the Bronsted acid salt is formed from the compound according to claim 1 and a Bronsted acid selected from the group consisting of a hydrohalic acid, perchloric acid, nitric acid, sulfuric acid, sulfonic acid, carboxylic acid, phenol, phosphoric acid, hexafluorophosphoric acid, boric acid, and tetrafluoroboric acid.

4. A method for producing the compound according to claim 1 , the method comprising reacting
a compound represented by general formula (2 A ):

wherein C is a carbon atom, N is a nitrogen atom, O is an oxygen atom, and S is a sulfur atom; and R 3 , Q 1 , and Q 2 are the same groups as R 3 , Q 1 , and Q 2 defined in claim 1 , with
a compound represented by general formula (4):

wherein H is a hydrogen atom and P is a phosphorus atom; L is lone pair electrons or boron trihydride; and R 1 and R 2 are the same groups as R 1 and R 2 defined in claim 1 .

5. A method for producing the compound according to claim 1 , the method comprising reacting
a compound represented by general formula (3 A ):

wherein C is a carbon atom, N is a nitrogen atom, O is an oxygen atom, and P is a phosphorus atom; L is lone pair electrons or boron trihydride; and R 1 , R 2 , Q 1 and Q 2 are the same groups as R 1 , R 2 , Q 1 and Q 2 defined in claim 1 , with
a compound represented by general formula (5):

wherein H is a hydrogen atom and S is a sulfur atom; and R 3 is the same group as R 3 defined in claim 1 .

6. A metal complex comprising the compound according to claim 1 as a ligand, wherein
the metal species is selected from the group consisting of group 8 transition metals, group 9 transition metals, and group 10 transition metals.

7. The metal complex according to claim 6 , wherein
the metal complex is represented by compositional formula (8 A ):
[M 8 X 1 X 2 (L 1 ) k (L 2 ) l (L 3 ) m (PNS)] n   (8 A ),

wherein M 8 is a divalent group 8 transition metal ion selected from the group consisting of a divalent iron ion, a divalent ruthenium ion, and a divalent osmium ion; X 1 and X 2 each independently are a monoanionic monodentate ligand, and L 1 , L 2 , and L 3 each independently are a neutral monodentate ligand; k, 1, and m, which respectively are the coordination numbers of L 1 , L 2 , and L 3 , each independently represent an integer of 0 or 1; PNS is the compound according to claim 1 ; and n, which is the degree of multimerization of the compositional formula: [M 8 X 1 X 2 (L 1 ) k (L 2 ) l (L 3 ) m (PNS)], is an integer of 1 or 2, provided that n is 1 when the total of k, l, and m is an integer of 1 to 3, and is 1 or 2 when the total is 0.

8. The metal complex according to claim 6 , wherein
the metal complex is represented by compositional formula (9 A ):
M 9 X 1 X 2 X 3 (L 1 ) k (L 2 ) l (L 3 ) m (PNS)  (9 A ),

wherein M 9 is a trivalent group 9 transition metal ion selected from the group consisting of a trivalent cobalt ion, a trivalent rhodium ion, and a trivalent iridium ion; X 1 , X 2 , and X 3 each independently are a monoanionic monodentate ligand, and L 1 , L 2 , and L 3 each independently are a neutral monodentate ligand; k, l, and m, which respectively are the coordination numbers of L 1 , L 2 , and L 3 , each independently are an integer of 0 or 1; and PNS is the compound according to claim 1 .

9. The transition metal complex according to claim 6 , wherein
the transition metal complex is represented by compositional formula (10 A ):
M 10 X 1 X 2 (L 1 ) k (PNS)  (10 A ),

wherein M 10 is a divalent group 10 transition metal ion selected from the group consisting of a divalent nickel ion, a divalent palladium ion, and a divalent platinum ion; X 1 and X 2 each independently are a monoanionic monodentate ligand, and L 1 is a neutral monodentate ligand; k, which is the coordination number of L 1 , is an integer of 0 or 1; and PNS is the compound according to claim 1 .

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Nakayama Yuji
• Ogata Osamu

Classifications

• C07F9/5077

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

• C07F9/5022 Primary

  Aromatic phosphines (P-C aromatic linkage) · CPC title

• C07F15/0053

  without a metal-carbon linkage · CPC title

• C07F9/5018

  Cycloaliphatic phosphines · CPC title

• C07F9/653

  Five-membered rings · CPC title