Method for producing endo-9-azabicyclo[3.3.1]nonan-3-ol derivative

Patent metadata

Field	Value
Publication number	US-2016200726-A1
Application number	US-201414913736-A
Country	US
Kind code	A1
Filing date	Aug 14, 2014
Priority date	Sep 6, 2013
Publication date	Jul 14, 2016
Grant date	—

Abstract

A 9-azabicyclo[3.3.1]nonan-3-one derivative is reacted with a hydrogen in the presence of a catalyst composed of a ruthenium complex to obtain, at a low cost, an endo-9-azabicyclo[3.3.1]nonan-3-ol derivative useful as a production intermediate for agrochemical agents or medicines.

First claim

1 . A method for producing a compound represented by formula (II), comprising reacting a compound represented by formula (I) with a hydrogen in a presence of a catalyst consisting of a ruthenium complex:

in the formulae (I) and (II), R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted alkoxycarbonyl group.

2 . The method according to claim 1 , wherein the ruthenium complex is a compound represented by the following formula: Ru(X)(Y)(Px) n (L) or Ru(X)(Y)(PN) 2 ,
in the formulae, X and Y each independently represents an anionic ligand, Px represents a phosphine ligand, n represents 1 or 2, L represents a ligand represented by the following formula (III) or a diamine ligand, and PN represents a ligand represented by the following formula (IV):

in the formulae, R 1 and R 2 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted aralkyl group,
a ring B represents an unsubstituted or substituted hetero ring,
a double line portion consisting of a continuous line and a dotted line represents a single bond or a double bond,
Z represents a coordinating atom selected from the group consisting of N, P, O, and S,
R 3 and R 4 each independently represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted aralkyl group, and
A represents an unsubstituted or substituted C1 to 4 alkylene group.

3 . The method according to claim 2 , wherein the ruthenium complex is a compound represented by the formula: Ru(X)(Y)(Px) n (L), and L represents a pyridin-2-yl methanamine, a (1-methyl-1H-benzimidazol-2-yl)methanamine, a (5-methylpyrazin-2-yl) methanamine, a benzoxazol-2-yl methanamine, a pyrimidin-2-yl methanamine, a thiazol-2-yl methanamine, or a (pyrazin-2-yl)methanamine.

4 . The method according to claim 2 , wherein the ruthenium complex is a compound represented by the formula: Ru(X)(Y)(Px) n (L), and L represents a diamine ligand represented by the following formula (VI);

wherein, R 5 to R 12 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted aralkyl group, two of R 5 to R 12 may be bonded together to from a ring, D represents a single bond, an unsubstituted or substituted alkylene group, an unsubstituted or substituted cycloalkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent hetero ring group.

5 . The method according to claim 2 , wherein the ruthenium complex is a compound represented by the formula: Ru(X)(Y)(PN) 2 , and PN represents a ligand represented by the following formula (V):

6 . The method according to claim 1 , wherein, in the formulae (I) and (II), R represents an unsubstituted or substituted aralkyl group, and the unsubstituted or substituted aralkyl group is a benzyl group.

Assignees

• Nippon Soda Co

Inventors

• Akashi Masaya
• Inoue Tsutomu
• Oooka Hirohito

Classifications

• C07D471/08 Primary

  Bridged systems · CPC title

• C07D451/14

  containing 9-azabicyclo [3.3.1] nonane ring systems, e.g. granatane, 2-aza-adamantane; Cyclic acetals thereof · CPC title

• C07C29/145

  with hydrogen or hydrogen-containing gases · CPC title

• B01J31/2447

  and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title