摘要:
The present invention provides a water-soluble transition metal-diamine complex which can be easily separated from reaction products through liquid separation, etc. and is recycleable; an optically active diamine compound constituting the ligand of the complex; and a catalyst for asymmetric synthesis which comprises these. The present invention relates to a water-soluble optically active transition metal-diamine complex represented by the formula (2): [wherein R1 and R2 each represents hydrogen, a hydrocarbon group, —SO2R13 (wherein R13 is a hydrocarbon group, substituted amino, etc.), etc.; R3 to R12 each represents hydrogen, a hydrocarbon group, alkoxy, substituted amino, etc.; M represents a transition metal; X represents halogen; L represents a ligand; and * indicates an asymmetric carbon atom; provided that at least one of R3 to R7 and R8 to R12 is substituted amino], a catalyst for asymmetric synthesis containing the complex, and a process for producing an optically active alcohol, which comprises using the catalyst to asymmetrically reduce a ketone.
摘要:
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.
摘要:
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.4 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.3 and R.sup.4 are bonded; and n is 1 or 2. The novel oxotitanium complex is useful as an asymmetric reaction catalyst. A process for producing a .beta.-hydroxy ketone or an .alpha.-hydroxy carboxylic acid ester in the presence of the novel oxotitanium complex is also disclosed.
摘要:
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.
摘要:
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).
摘要:
2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl represented by formula (I). ##STR1## is disclosed. A transition metal complex containing the same, a process for producing 2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl, and a process for producing 2,2'-bis(diphenylphosphinyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl are also disclosed.
摘要:
A process for producing an optically active dihydropyran derivative represented by formula (1): ##STR1## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 each represents a hydrogen atom, a lower alkyl group, a tri-lower alkylsilylmethyl group, a lower alkoxycarbonylamino group, or an --OR.sup.5 group, wherein R.sup.5 represents a lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a di-lower alkylcarbamoyl group, or a tri-lower alkylsilyl group, or R.sup.1 and R.sup.2 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, or R.sup.2 and R.sup.3 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, provided that all of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 do not represent hydrogen atoms at the same time; and R.sup.6 represents a lower alkyl group, which comprises reacting a diene compound represented by formula (2): ##STR2## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the same meanings as defined above, with a glyoxylic acid ester represented by formula (3): ##STR3## wherein R.sup.6 has the same meaning as defined above, in the presence of a binaphthol-titanium complex represented by formula (4): ##STR4## wherein X represents a chlorine atom or a bromine atom, is disclosed.
摘要:
A process for preparing an optically active alcohol is disclosed, which comprises asymmetrically hydrogenating a carbonyl compound in the presence of a ruthenium-optically active phosphine complex as a catalyst. The resulting alcohol has high optical purity.
摘要:
Disclosed is a selective ester production process of an alcoholic hydroxyl group, which proceeds under chemically mild conditions, while having adequate environmental suitability, operability and economical efficiency. Specifically disclosed is a process for producing an ester compound, which is characterized in that an alcohol and a carboxylic acid ester compound are reacted in the presence of a compound containing zinc element, thereby selectively acylating a hydroxyl group of the alcohol.
摘要:
Provided is a method for producing a ruthenium complex comprises the step of reacting a ruthenium compound represented by general formula (1): [RuX(L)(PP)]X (1), wherein Ru represents a ruthenium atom; X represents a halogen atom; L represents an arene; and PP represents an optically active bisphosphine, with a carboxylate salt represented by general formula (2): R1CO2M (2), wherein M represents a monovalent cation; and R1 represents a group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups, to produce a ruthenium complex represented by general formula (3): Ru(OCOR1)2(PP) (3), wherein R1 represents the group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups; and PP represents the optically active bisphosphine.