N-N-bis(2-dialkylphosphinoethyl)amine-borane complex and production method therefor, and method for producing ruthenium complex containing N,N-bis(2-dialkylphosphinoethyl)amine as ligand

Patent metadata

Field	Value
Publication number	US-10407448-B2
Application number	US-201716073660-A
Country	US
Kind code	B2
Filing date	Jan 30, 2017
Priority date	Jan 29, 2016
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The purpose of the present invention is to provide an N,N-bis(2-dialkylphosphinoethyl)amine-borane complex which is a ruthenium complex that exhibits excellent catalytic activity in a hydrogenation reaction, etc., and a production method therefor, and a method for efficiently producing a ruthenium complex containing N,N-bis(2-dialkylphosphinoethyl)amine as a ligand. The present invention is capable of efficiently producing an amine-borane complex (3) by reacting an oxazolidinone compound (1) with a dialkylphosphine-borane compound (2) in the presence of a base. The present invention is also capable of efficiently producing a ruthenium complex (5) by reacting the amine-borane complex (3) with a ruthenium compound (4) in the presence of an amine.

(In the formula, a solid line, a dashed line, B, C, H, L 1 -L 3 , LG, n, N, O, P, Ru, X, and R 1 -R 10 are as defined in the description.)

First claim

The invention claimed is:

1. A method for producing a compound having the following formula (3):

wherein the solid line represents a single bond; B represents a boron atom, C represents a carbon atom, H represents a hydrogen atom, N represents a nitrogen atom, and P represents a phosphorus atom; R 1 and R 2 each independently represent an optionally substituted alkyl group or an optionally substituted cycloalkyl group, wherein R 1 and R 2 , which are adjacent to each other, may bind together to form an optionally substituted ring; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom or a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group, wherein any two of R 3 to R 10 may bind together to form an optionally substituted ring; n=2 to 3, and BH 3 is coordinated to a nitrogen atom or phosphorus atom, the method comprising: reacting a compound having the following formula (1):

wherein the solid line represents a single bond, and the double line represents a double bond; C represents a carbon atom, N represents a nitrogen atom, and O represents an oxygen atom; LG represents a leaving group; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom or a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group, wherein any two of R 3 to R 10 may bind together to form an optionally substituted ring, with a phosphorus compound having the following formula (2):

wherein the solid line represents a single bond, and the dashed line represents a coordination bond; B represents a boron atom, H represents a hydrogen atom, and P represents a phosphorus atom; R 1 and R 2 each independently represent an optionally substituted alkyl group or an optionally substituted cycloalkyl group, wherein R 1 and R 2 may bind together to form an optionally substituted ring, in the presence of bases.

2. The method according to claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen atoms.

3. The method according to claim 1 or 2 , wherein R 1 and R 2 are groups each independently selected from the group consisting of an isopropyl group, a cyclohexyl group, and a tert-butyl group.

4. The method according to claim 1 , wherein LG is a halogen atom or a group selected from the group consisting of a methanesulfonyloxy group (OMs), a p-toluenesulfonyloxy group (OTs), a benzenesulfonyloxy group (OSO 2 C 6 H 5 ), and a trifluoromethanesulfonyloxy group (OTf).

5. The method according to claim 1 , wherein one of the bases is an alkyllithium.

6. A method for producing a ruthenium complex having the following formula (5):

wherein the solid line represents a single bond, the triple line represents a triple bond, and the dashed line represents a coordination bond; C represents a carbon atom, H represents a hydrogen atom, N represents a nitrogen atom, O represents an oxygen atom, P represents a phosphorus atom, and Ru represents a ruthenium atom; X represents an anionic group; R 1 and R 2 each independently represent an optionally substituted alkyl group or an optionally substituted cycloalkyl group, wherein R 1 and R 2 , which are adjacent to each other, may bind together to form an optionally substituted ring; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom or a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group, wherein any two of R 3 to R 10 may bind together to form an optionally substituted ring, the method comprising: reacting a compound having the following formula (3):

wherein the solid line represents a single bond; B represents a boron atom, C represents a carbon atom, H represents a hydrogen atom, N represents a nitrogen atom, and P represents a phosphorus atom; R 1 and R 2 each independently represent an optionally substituted alkyl group or an optionally substituted cycloalkyl group, wherein R 1 and R 2 , which are adjacent to each other, may bind together to form an optionally substituted ring; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom or a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group, wherein any two of R 3 to R 10 may bind together to form an optionally substituted ring; n=2 to 3, and BH 3 is coordinated to a nitrogen atom or phosphorus atom, with a ruthenium compound having the following formula (4):

wherein the solid line represents a single bond, the triple line represents a triple bond, and the dashed line represents a coordination bond; C represents a carbon atom, H represents a hydrogen atom, O represents an oxygen atom, and Ru represents a ruthenium atom; X represents an anionic group; and L 1 , L 2 , and L 3 each independently represent a monodentate ligand, in the presence of amines.

7. The method according to claim 6 , wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen atoms.

8. The method according to claim 6 or 7 , wherein R 1 and R 2 are groups each independently selected from the group consisting of an isopropyl group, a cyclohexyl group, and a tert-butyl group.

9. The method according to claim 6 , wherein L 1 , L 2 , and L 3 are tertiary phosphines.

10. The method according to claim 6 , wherein X is a halogen atom.

11. A compound having the following formula (3):

wherein the solid line represents a single bond; B represents a boron atom, C represents a carbon atom, H represents a hydrogen atom, N represents a nitrogen atom, and P represents a phosphorus atom; R 1 and R 2 each independently represent an optionally substituted alkyl group or an optionally substituted cycloalkyl group, wherein R 1 and R 2 , which are adjacent to each other, may bind together to form an optionally substituted ring; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom or a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group, wherein any two of R 3 to R 10 may bind together to form an optionally substituted ring; n=2

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Nakayama Yuji
• Nakajima Hikaru

Classifications

• C07F9/5027

  Polyphosphines · CPC title

• C07F5/022

  without C-boron linkages · CPC title

• C07F9/5077 Primary

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

• C07F15/0046

  Ruthenium compounds · CPC title

• C07F9/28

  with one or more P—C bonds · CPC title