Abstract: Disclosed is a ruthenium-phosphine complex usable as the catalyst giving a high enantiomer excess in an asymmetric reaction and a method for producing the complex. The ruthenium-phosphine complex is represented by formula (1): [{(RuX(L)}2(&mgr;-X)3]−[R22NH2]+  (1) wherein R2 represents hydrogen, alkyl, cycloalkyl or benzyl and L represents a diphosphine ligand represented by formula (2): wherein R1 represents an optionally substituted phenyl group and X represents a halogen atom. The method for preparing a ruthenium-phosphine complex represented by formula (1) is characterized in that a ruthenium complex represented by the formula [RuX(arene)(L)]X and an ammonium salt represented by the formula R22NH.HX are reacted with each other.

Abstract: Disclosed is a process for producing an optically active .beta.-lactone represented by the general formula (I): ##STR1## wherein R.sup.1 represents an alkyl group having 1-9 carbon atoms which can be branched or a cycloalkyl group having 5-7 carbon atoms. The process comprises reacting an aldehyde represented by the general formula (II):R.sup.1 CHO (II)wherein R.sup.1 is the same as defined above, with a ketene represented by the general formula (III):CH.sub.2 .dbd.C.dbd.O (III)in the presence of a bissulfonamide/aluminum complex represented by the general formula (IV): ##STR2## wherein Ar represents 2,4,6-(R.sup.2).sub.3 C.sub.6 H.sub.2 (wherein R.sup.2 represents an alkyl group having 2-4 carbon atoms), Et represents an ethyl group and Ph represents a phenyl group.

Abstract: The present invention provides a method for making compound (1) by reacting compound (2) with phosphine oxide (3) in the presence of a transition metal/phosphine complex and optionally reducing the reaction product: ##STR1## where n represents 0 or 1; the double line having a continuous line and a dotted line represents a double bond or a single bond such that the ring having the double line forms a naphthalene ring or an octahydronaphthalene ring with an adjacent benzene ring; Tf represents a trifluoromethanesulfonyl group; and Ar represents a phenyl group, a substituted phenyl group or a naphthyl group. The present invention provides an economical way to produce compound (1) as a ligand of a complex useful as a catalyst for a variety of asymmetric synthesis reactions.

Abstract: Disclosed is a ruthenium-phosphine complex represented by formula (I):?{RuX(L)}.sub.2 (.mu.-X).sub.3 !.sup.- ?R.sub.2 NH.sub.2 !.sup.+(I)wherein R is hydrogen, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; X is halogen; and L is an optically active or inactive tertiary phosphine. A process for preparing the complex (I) is also disclosed, which comprises (A) reacting a ruthenium complex represented by formula: ?RuX(arene)(L)!X (wherein arene is a substituted or unsubstituted phenyl group) and an ammonium salt represented by formula (III): R.sub.2 NH.HX, or (B) reacting a ruthenium complex represented by formula: ?RuX.sub.2 (arene)!.sub.2, a tertiary phosphine represented by L, and an ammonium salt (III). The complex (I) useful as a catalyst for general syntheses or asymmetric syntheses can be obtained easily in good yield.

Abstract: The present invention provides a ligand for a novel catalyst superior in such characteristics as selectivity (chemoselectivity and enantioselectivity) and catalytic activity in asymmetric synthesis reactions and a ligand for a novel catalyst effective in an asymmetric hydrogenation reaction in particular. The ligand is an optically active diphosphine compound represented by the following formula: ##STR1## where Ph is a phenyl group, X is a chlorine or bromine atom, and R.sup.1 and R.sup.2 are each an alkyl group having 1 to 3 carbon atoms.

Abstract: A novel chiral unsymmetric diphosphine compound of formula (I): ##STR1## wherein Ar.sup.1 and Ar.sup.2, which are different from each other, each represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a furfuryl group, a benzofurfuryl group, a thienyl group, or a benzothienyl group, and a transition metal complex containing the diphosphine compound as a ligand. The complex catalyzes various asymmetric synthesis reactions, e.g., asymmetric hydrogenation or asymmetric hydrosilylation, exhibiting excellent performance in selectivity, conversion and catalytic activity, to provide a product of desired absolute configuration at high optical purity and in high yield.

Abstract: Disclosed are an optically active diphosphine represented by formula: ##STR1## wherein R represents a lower alkyl group having 1 to 4 carbon atoms; Ar represents a phenyl group which may be substituted with a lower alkyl group having 1 to 4 carbon atoms and/or a lower alkoxy group having 1 to 4 carbon atoms, a transition metal complex containing the diphosphine as a ligand, and a process for producing an optically active .delta.-oxo-.alpha.-cyano ester using the transition metal complex as a catalyst.

Abstract: A novel oxotitanium complex represented by general formula (I) is disclosed: ##STR1## wherein R.sup.1 and R.sup.2 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a phenyl group, a substituted phenyl group, a trialkylsilyl group, a monoalkyldiphenylsilyl group, a dialkylmonophenylsilyl group, a triphenylsilyl group, a substituted triphenylsilyl group, or a lower alkoxycarbonyl group, provided that R.sup.1 and R.sup.2 may be bonded to each other to form a hydrocarbon ring or a substituted hydrocarbon ring in cooperation with the carbon atoms to which R.sup.1 and R.sup.2 are bonded; R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a benzoyl group, a benzenesulfonyl group, or a halogen atom, provided that R.sup.3 and R.sup.

Abstract: A novel oxotitanium complex represented by general formula (I) is disclosed: ##STR1## wherein R.sup.1 and R.sup.2 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a phenyl group, a substituted phenyl group, a trialkylsilyl group, a monoalkyldiphenylsilyl group, a dialkylmonophenylsilyl group, a triphenylsilyl group, a substituted triphenylsilyl group, or a lower alkoxycarbonyl group, provided that R.sup.1 and R.sup.2 may be bonded to each other to form a hydrocarbon ring or a substituted hydrocarbon ring in cooperation with the carbon atoms to which R.sup.1 and R.sup.2 are bonded; R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a benzoyl group, a benzenesulfonyl group, or a halogen atom, provided that R.sup.3 and R.sup.

Abstract: The present invention provides a method for producing novel optically active diphosphine compounds ?2,2'-bis(di-substituted phosphino)-1,1'-binaphthyl compounds! having a selectivity (chemoselectivity or enantioselectivity) and catalytic activity different from those of conventional BINAP compounds. In a method of the present invention for producing an optically active diphosphine compound (i.e., 2,2-bis(di-substituted phosphino)-1,1'-binaphthyl), 2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthyl is reacted, in the presence of a transition metal-phosphine complex, with a phosphineoxide compound represented by the following general formula:A.sub.

Abstract: Disclosed herein is a process for producing a (2S,5S)-2,5-diamino-1,6-diphenyl-3-hexanone derivative represented by the formula (1): ##STR1## wherein R.sup.1 means a lower alkylcarbonyl group, a halogen-substituted lower alkylcarbonyl group, an arylcarbonyl group or a lower alkoxycarbonyl group, and R.sup.2 and R.sup.3 are identical with or different from each other and denote individually an aryl group or an alkoxy-substituted aryl group, which comprises subjecting a (2S)-2,5-diamino-1,6-diphenyl-4-hexen-3-one derivative represented by the formula (2): ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 have the same meaning as defined above, to a hydrogenation reaction in the presence of a transition metal-containing catalyst.

Abstract: A novel oxotitanium complex represented by general formula (I) is disclosed: ##STR1## wherein R.sup.1 and R.sup.2 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a phenyl group, a substituted phenyl group, a trialkylsilyl group, a monoalkyldiphenylsilyl group, a dialkylmonophenylsilyl group, a triphenylsilyl group, a substituted triphenylsilyl group, or a lower alkoxycarbonyl group, provided that R.sup.1 and R.sup.2 may be bonded to each other to form a hydrocarbon ring or a substituted hydrocarbon ring in cooperation with the carbon atoms to which R.sup.1 and R.sup.2 are bonded; R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a benzoyl group, a benzenesulfonyl group, or a halogen atom, provided that R.sup.3 and R.sup.

Abstract: A process for preparing an optically active (2S,3S)-allophenylnorstatin derivative (I) is disclosed, comprising asymmetrically hydrogenating a 4-phenyl-2-halogeno-3-oxobutyric ester (III) in the presence of a ruthenium-phosphine complex to obtain a 4-phenyl-(2S)-halogeno-(3R)-hydroxybutyric ester (IV), epoxidizing the ester (IV) in the presence of a base to obtain a 4-phenyl-(2S,3R)-epoxybutyric ester (V), reacting the ester (V) with a tri(lower alkyl)silylazide or a (lower alkyl)diarylsilylazide in the presence of a Lewis to obtain a (3S)-azido-4-phenyl-(2S)-trisubstituted silyloxybutyric ester (VI), hydrogenolyzing the ester (VI) into a (2S,3S)-allophenylnorstatin derivative (VII), protecting the amino group of the compound (VII), and, if desired, hydrolyzing the compound before or after the amino group protection. Compounds (I) can be obtained at high optical purity safely and in good yield.

Abstract: A process for the production of an optically active carboxylic acid (I), which comprises subjecting an olefinic carboxylic acid (II) to asymmetric hydrogenation using a complex as a catalyst consisting of an optically active phosphine (III) and a ruthenium compound.Complex of ##STR1## with a ruthenium compound ##STR2## According to the process of the present invention, optically active carboxylic acids can be produced with high yield.

Abstract: A phosphine compound represented by one of the formulas: ##STR1## wherein R.sup.1 and R.sup.2, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a halogen atom or a lower alkyl group or taken together form a divalent hydrocarbon group; and R.sup.3 and R.sup.4, which may be the same or different, each represent a lower alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, a lower alkyl group or a lower alkoxy group or taken together form a divalent hydrocarbon group, and wherein R.sup.6 and R.sup.6' which may be the same or different, each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group; R.sup.5, R.sup.5', R.sup.11 and R.sup.11' which may be the same or different, each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; or a pair of R.sup.5 and R.sup.6 or a pair of R.sup.5' and R.sup.6' may form a ring; R.sup.7 and R.sup.

Abstract: Disclosed herein is a process for producing a (2S,5S)-2,5-diamino-1,6-diphenyl-3-hexanone derivative represented by the formula (1): ##STR1## wherein R.sup.1 means a lower alkylcarbonyl group, a halogen-substituted lower alkylcarbonyl group, an arylcarbonyl group or a lower alkoxycarbonyl group, and R.sup.2 and R.sup.3 are identical with or different from each other and denote individually an aryl group or an alkoxy-substituted aryl group, which comprises subjecting a (2S)-2,5-diamino-1,6-diphenyl-4-hexen-3-one derivative represented by the formula (2): ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 have the same meaning as defined above, to a hydrogenation reaction in the presence of a transition metal-containing catalyst.

Abstract: A process for for producing a (2R,3S)-cyclohexylnorstatine or a salt thereof is disclosed, which comprises the steps of: enantioselectively hydrogenating a 4-cyclohexyl-2-halogeno-3-oxobutyric acid ester in the presence of a ruthenium-phosphine complex to produce a 4-cyclohexyl-2-halogeno-(3R)-hydroxybutyric acid ester (2); epoxidizing the compound (2) in the presence of a base to produce a 4-cyclohexyl-(2S,3R)-epoxybutyric acid ester (3); reacting the compound (3) with a lower trialkylsilyl azide in the presence of a Lewis acid to produce a (3S)-azide-4-cyclohexyl-(2S)-substituted butyric acid ester (4); subjecting the compound (4) to hydrogenolysis to produce a (2S,3S)-cyclohexylnorstatine derivative (5); and inverting the configuration at the 2-position of the compound (5).

Abstract: A process for for producing a (2R,3S)-cyclohexylnorstatine or a salt thereof is disclosed, which comprises the steps of: enantioselectively hydrogenating a 4-cyclohexyl-2-halogeno-3-oxobutyric acid ester in the presence of a ruthenium-phosphine complex to produce a 4-cyclohexyl-2-halogeno-(3R)-hydroxybutyric acid ester (2); epoxidizing the compound (2) in the presence of a base to produce a 4-cyclohexyl-(2S,3R)-epoxybutyric acid ester (3); reacting the compound (3) with a lower trialkylsilyl azide in the presence of a Lewis acid to produce a (3S)-azide-4-cyclohexyl-(2S)-substituted butyric acid ester (4); subjecting the compound (4) to hydrogenolysis to produce a (2S,3S)-cyclohexylnorstatine derivative (5); and inverting the configuration at the 2-position of the compound (5).

Abstract: A process for producing an optically active .beta.-hydroxyketone represented by formula (I): ##STR1## by catalytic asymmetrical aldol reaction is disclosed, comprising reacting a silyl-enol ether represented by formula (II): ##STR2## with a substituted aldehyde represented by formula (III):R.sup.5 CHO (III)in the presence of a binaphthol-titanium complex represented by formula (IV): ##STR3## An optically active .beta.-hydroxyketone is efficiently produced with diastereo-specificity and enantio-specificity.

Abstract: 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.