Nagoya University

Takasago International Corporation

Showa Denko K.k.

Takasago Perfumery Co., Ltd.

Masato Kitamura

Ryoji Noyori

Hidenori Kumobayashi

Noboru Sayo

Naoya Fukumoto

Takeshi Ohkuma

Yoshitaka Ishibashi

Toshiaki Noda

Susumu Akutagawa

Hidemasa Takaya

Martin F Giles

Shinji Tanaka

Masumi Katsuki

Naoki Kanda

Masahiro Yoshimura

Hideko Natsume

Makoto Tokunaga

Provided is a method for producing a 2-alkenylamine compound efficiently and at low cost, using a primary or secondary amine compound and a 2-alkenyl compound as the starting materials therefor. The 2-alkenylamine compound is produced by adding Bronsted acid when 2-alkenylating by reacting the primary or secondary amine compound with the 2-alkenyl compound, and 2-alkenylating in the presence of a catalyst comprising a complexing agent and a transition metal precursor stabilized by a monovalent anionic five-membered conjugated diene.

Production method for 2-alkenylamine compound

Provided is a method for producing a 2-alkenylamine compound efficiently and at low cost, using a primary or secondary amine compound and a 2-alkenyl compound as the starting materials therefor. The 2-alkenyleamine compound is produced by 2-alkenylating a primary or secondary amine compound, using a specified 2-alkenylating agent and in the presence of a catalyst comprising a complexing agent and a transition metal precursor stabilized by a monovalent anionic five-membered conjugated diene.

Disclosed are: a ligand for an asymmetric synthesis catalyst; and a process for producing an &#x3b1;-alkenyl cyclic compound using the ligand. Specifically disclosed are: a ligand for an asymmetric synthesis catalyst, which is represented by any one of formulae (1) to (4) [wherein Rrepresents &#x2014;Cl or &#x2014;Br; Rrepresents &#x2014;CHor &#x2014;CF; and Rrepresents &#x2014;CH&#x2014;CH&#x2550;CHor &#x2014;H]; and a process for producing an &#x3b1;-alkenyl cyclic compound using the ligand. 

Ligand for asymmetric synthesis catalyst, and process for production of alpha-alkenyl cyclic compound using the same

The evacuation and inert gas introduction apparatus capable of quickly switching over between the evacuation state and the inert gas introduction state, is provided for a synthesizing device for molecular asymmetrical catalysts. The evacuation line is connected to a vacuum pump via a cock and solvent trap. The inert gas introduction line is connected to an argon gas cylinder via a cock. The vacuum cavity is provided at a tip end of the housing of the three-way cock, and thus the inside plug is attracted towards the vacuum cavity. The evacuation line is connected to the first port of the three-way cock, the inert gas introduction line is connected to the second port and the each reaction chamber of the synthesizing apparatus is connected to the third port. As the rotation angle of the inside plug is changed, the connection state of the line is switched.

Evacuation and inert gas introduction apparatus

The object of the invention is to provide a solvent distillation apparatus capable of preparing a highly pure anoxic, dehydrated solvent. A distilling flask is connected to a vacuum double-barrel fractionating column by a glass flange. The upper end of the fractionating column is connected to a middle portion of a reflux condenser. The upper end of the reflux condenser is provided with an outlet for a purge gas, and the lower end thereof is connected to a condensate reservoir. The base of the condensate reservoir is connected to the fractionating column near a lower end thereof via a Young cock, and also connected to a collecting flask via a Young cock and a glass flange. An immersion tube is used to blow an inactive gas into a base portion of the condensate reservoir. The fractionating column, the reflux condenser and the condensate reservoir are integrated as one body.

Solvent distillation apparatus

Disclosed is a method of producing an optically active &bgr;-hydroxy sulfonic acid compound comprising hydrogenating a &bgr;-keto sulfonic acid compound represented by formula 1:

Method of producing an optically active &bgr;-hydroxy sulfonic acid compound by catalytic asymmetric hydrogenation

Disclosed herein is a process for producing an optically active hydroxyalkylphosphonate represented by the formula (4), which comprises asymmetrically hydrogenating an oxoalkylphosphonate represented by the formula (1) using, as a catalyst, a ruthenium-optically active phosphine complex represented by the formula (2). ##STR1##

Process for producing optically active hydroxyalkylphosphonates

A process for producing an optically active .gamma.-butyrolactone derivative represented by formula (II): ##STR1## wherein R.sup.1 represents an alkyl group having from 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group; and * indicates an asymmetric carbon atom, is disclosed, comprising enantioselectively hydrogenating a .gamma.-keto acid or an ester thereof represented by formula (I): ##STR2## wherein R.sup.1 and * are as defined above; and R.sup.2 represents a hydrogen atom or a lower alkyl group, in the presence of an optically active ruthenium-phosphine complex. The compounds (I) can be obtained at high optical purity through simple operations and a reduced number of steps.

Process for producing optically active .gamma.-butyrolactone derivatives

A ruthenium-phosphine complex represented by formula (I): ##STR1## wherein R.sup.2 -BINAP represents a teritary phosphine compound represented by formula (II): ##STR2## wherein R.sup.2 represents a hydrogen atom, a methyl group, a methoxy group, or a t-butyl group; X represents a halogen atom; and R and R.sup.1, which may be the same or different, each represent a phenyl group or a substituted phenyl group, and a ruthenium-phosphine complex represented by formula (III): ##STR3## wherein R and R.sup.1 are as defined above; and dma represents N,N-dimethylacetamide, which is an intermediate for synthesizing the ruthenium-phosphine complex of formula (I), are disclosed. The complex of formula (I) is useful as a catalyst for general syntheses with its ligand being an optically inactive compound or for asymmetric syntheses with its ligand being an optically active compound and, also, can be prepared at a low cost.

Ruthenium-phosphine complex and intermediate for producing the same

A process for preparing carnitine which comprises asymmetrically hydrogenating a .gamma.-halogeno-.beta.-keto ester represented by formula (I): ##STR1## wherein X represents a chlorine atom or a bromine atom; and R represents a lower alkyl group, in the presence of a ruthenium-optically active phosphine complex represented by formula (II), (III) or (IV):

Process for preparing carnitine

A process for preparing an N-acyltetrahydroisoquinoline represented by formula (II) ##STR1## wherein A represents a phenylene ring substituted with a hydroxyl group, a lower alkoxy group, an acetoxy group, or a benzyloxy group; R represents a hydrogen atom, a lower alkyl group, or a phenyl group; and X represents a hydrogen atoms, a phenyl group, or a phenyl group substituted with a hydroxyl group, a lower alkoxy group, or an acetoxy group, which comprises asymmetrically hydrogenating an N-acyl-1-methylenetetrahydroisoquinoline or N-acyl-1-benzylidenetetrahydroisoquinoline represented by formula (I) ##STR2## wherein A, R, and X are as defined above, in the presence of an optically active ruthenium-phosphine complex as a catalyst. The process exclusively and efficiently provides a useful isomer of the N-acyltetrahydroisoquinoline of high purity which is useful as an intermediate for synthesizing isoquinoline type alkaloids as pharmaceuticals without involving optical resolution of a racemate.

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Nagoya, Japan

Masato Kitamura