US 7,619,003 B2 · Process for producing optically active compound

Abstract

A process for producing an optically active compound based on the hydrolysis of an alkenyl ester compound or the cleavage of an alkenyl ether compound. The process uses neither an acidic compound nor a basic compound, and reactants can be reacted in a high concentration. It does not necessitate a buffer, nutrient, etc. unlike enzymatic reactions or reactions using a microorganism. It is a simple process which attains a satisfactory production efficiency. The process, which is for producing an optically active carboxylic acid or optically active alcohol represented by the general formula (VI): (wherein R1, R2, and R3 are different groups; and A represents methylene, carbonyl, or a single bond), is characterized by causing water to act on an alkenyl ester or alkenyl ether represented by the general formula (I): (wherein R4, R5, and R6 each represents hydrogen, alkyl, etc.) in the presence of a specific transition metal complex having an optically active ligand.

A process for producing an optically active compound represented by the following formula (VI), the process comprising reacting water with a compound represented by the following formula (I) in the presence of one or more transition metal complexes having, as a ligand, an optically active compound represented by the following formula (III):

wherein R1, R2 and R3, which are different from each other, represent
a hydrogen atom,
a straight-chain, branched-chain or cyclic alkyl group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine,
a straight-chain or branched-chain alkoxy group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine,
an aralkyl group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine,
an aryl group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine,
an aralkyloxy group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine,
an alkylthio group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine, or
an aralkylthio group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine;
any two of R1, R2 and R3 optionally form a ring;
and
R4, R5 and R6 each independently represent a hydrogen atom, or a straight-chain, branched-chain or cyclic alkyl group optionally substituted with alkyl, alkoxy, halogen, trifluoromethyl, phenyl, benzyl, hydroxyl, alkoxycarbonyloxy, benzoyl, benzyloxy, methoxymethyl, 2H-tetrahydropyran-2-yloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, benzyloxycarbonyloxy, oxirane-2-yl, 1,3-dioxolan-4-yl, 2-oxo-1,3-dioxolan-yl, amino, dimethylamino, diethylamino, acetoxyamino, benzyloxycarbonylamine, aniline or benzylamine, R4 and R5 or R5 and R6 are optionally combined with each other together with an adjacent carbon atom having a double bond to form a ring;
and A represents a carbonyl group or a single bond;
wherein R11 and R12 each independently represent a hydrogen atom or a methyl group, R13, R14, R15 and R16 each independently represent a hydrogen atom or an alkyl group and, * represents an asymmetric carbon atom;
wherein R1, R2 and A have the same meanings as above, and * represents an asymmetric carbon atom.

12 more elements

Process for producing optically active compound

Life of this patent

Process for producing optically active compound

Life of this patent

Abstract

Claims9