Title of Invention	AN ASYMMETRIC COPPER COMPLEX AND A PROCESS FOR MAKING THE SAME
Abstract	A process for production of an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or the like and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): wherein R10 is as described above, in the presence of an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound. (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 represent a C1-C6 alkyl group or the like; R3 represents a tert-butyl group or the like; and R4 and R5 are the same and represent C1-C3 alkyl groups or the like, and (C) at least one boron compound represented by the formula (2): wherein A represents a trityl group or the like, X represents a fluorine atom or the like, and n represents an integer of 1 to 5.

Title of Invention

AN ASYMMETRIC COPPER COMPLEX AND A PROCESS FOR MAKING THE SAME

Abstract

A process for production of an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or the like and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): wherein R10 is as described above, in the presence of an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound. (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 represent a C1-C6 alkyl group or the like; R3 represents a tert-butyl group or the like; and R4 and R5 are the same and represent C1-C3 alkyl groups or the like, and (C) at least one boron compound represented by the formula (2): wherein A represents a trityl group or the like, X represents a fluorine atom or the like, and n represents an integer of 1 to 5.

Full Text	DESCRIPTION PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE CYCLOPROPANECARBOXYLATE COMPOUND Technical Field The present invention relates to a process for production of an optically active cyclopropanecarboxylate compound. Background Art Optically active cyclopropanecarboxylate compounds whose representative examples are (+)-trans-2,2-dimethy1-3- (2-methy1-1-propenyl)cyclopropanecarboxylate and (+)-trans- 3,3-dimethy1-2-(acetoxymethyl)cyclopropanecarboxylate are important compounds as synthetic intermediates of pesticides and pharmaceuticals such as synthesized pyrethroid insecticides and methods for producing it are described in EP 895992 A, US 6858559, Tetrahedron Lett., 32, 7373 (1991), Tetrahedron, 57, 6083 (2001) and the like. Disclosure of the Invention The present invention provides an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound, (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 are the same or different, and independently represent a hydrogen atom; a C1-C6 alkyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups, or R1 and R2 are bonded together to represent a C2-C6 polymethylene group, R3 represents a methyl group; an isopropyl group; an isobutyl group; a tert-butyl group; a 1-naphthyl group; a 2-naphthyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups, and R4 and R5 are the same and represent hydrogen atoms or C1- C3 alkyl groups, or R4 and R5 are bonded together to represent a C2-C5 polymethylene group, and (C) at least one boron compound represented by the formula (2): wherein A represents a lithium atom, a sodium atom, a potassium atom, a silver atom or a trityl group, X represents a fluorine atom or a fluorine-substituted C1-C8 alkyl group, and X represents an integer of 1 to 5, and a process for production of an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 are the same or different, and independently represent a hydrogen atom; a halogen atom; a C1-C6 alkyl group which is optionally substituted with a halogen atom or atoms, a C1-C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2-C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C6-C10 aryloxycarbonyloxy group or groups; a C1-C6 alkenyl group which is optionally substituted with a halogen atom or atoms or a C2-C7 alkoxycarbonyl group or groups; a C6- C10 aryl group which is optionally substituted with a C1-C6 alkoxy group or groups; a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups; or a C2-C7 alkoxycarbonyl group which is optionally substituted with a halogen atom or atoms, a C1-C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2- C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C6-C10 aryloxycarbonyloxy group or groups; provided that, when R6 and R8 represent the same, R6 and R7 represent different groups each other; and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): wherein R10 is as described above, in the presence of the asymmetric copper complex. Best Mode for Carrying Out the Present Invention Examples of the monovalent or divalent copper compound which is component (A) include copper(I) trifluoromethanesulfonate, copper(I) acetate, copper(I) bromide, copper(I) chloride, copper(I) iodide, copper(I) hydroxide, copper(II) trifluoromethanesulfonate, copper(II) acetate, copper(II) bromide, copper(II) chloride, copper(II) iodide and copper(II) hydroxide and the monovalent copper compound is preferable. A copper halide compound such as copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(II) chloride, copper(II) bromide and copper(II) iodide is preferable. These copper compounds may be used alone, or two or more kinds thereof may be used. As the monovalent or divalent copper compound, a commercially available compound can be used as it is. A monovalent copper compound prepared by contacting the divalent copper compound with a reducing agent such as phenylhydrazine may be used. A monovalent copper compound may be generated to use by contacting the divalent copper compound with a reducing agent such as phenylhydrazine in the reaction system. In the formula of the optically active bisoxazoline compound represented by the formula (1) (hereinafter, simply referred to as the optically active bisoxazoline compound (1)) which is the component (B) , R1 and R2 are the same or different, and independently represent a hydrogen atom; a C1-C6 alkyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups, or R1 and R2 are bonded together to represent a C2-C6 polymethylene group. Examples of the C1-C6 alkyl group include a straight or branched chain alkyl group such as a methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and n-hexyl group. Examples of the C1-C6 alkoxy group include a straight or branched chain alkoxy group such as a methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, and n-hexyloxy group. Examples of the phenyl group which is optionally substituted with the C1-C6 alkyl group or groups or the C1- C6 alkoxy group or groups include a phenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl and 4- methoxyphenyl group. Examples of the C7-C12 aralkyl group which is optionally substituted with the C1-C6 alkoxy group or groups include a benzyl, 2-methylbenzyl, 3-methylbenzyl, 4- methylbenzyl, (1-naphthyl)methyl, (2-naphthyl)methyl, 2- methoxybenzyl, 3-methoxylbenzyl and 4-methoxybenzyl group. When R1 and R2 are bonded together to represent the C2-C6 polymethylene group, examples of the C2-C6 polymethylene group include an ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene group. R3 represents a methyl group; an isopropyl group; an isobutyl group; a tert-butyl group; a 1-naphthyl group; a 2-naphthyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups, or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups. Examples of the phenyl group which is optionally substituted with the C1-C6 alkyl group or groups, or the C1-C6 alkoxy group or groups and the C7-C12 aralkyl group which is optionally substituted with the C1-C6 alkoxy group or groups include the same groups as those exemplified above. R4 and R5 are the same and represent hydrogen atoms or C1-C3 alkyl groups, or R4 and R5 are bonded together to represent a C2-C5 polymethylene group. Examples of the C1-C3 alkyl group include a methyl, ethyl, n-propyl and isopropyl group. When R4 and R5 are bonded together to represent the C2-C5 polymethylene group, examples of the C2-C5 polymethylene group include an ethylene, trimethylene, tetramethylene and pentamethylene group. Examples of the optically active bisoxazoline compound (1) include bis[2-[(4S)-methyloxazoline]]methane, bis[2- t(4S)-methy1-5,5-dimethyloxazoline]]methane, bis[2-[(4S)- methy1-5,5-diethyloxazoline]]methane, bis[2-[(4S)-methy1- 5,5-di(n-propyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5- diphenyloxazoline]]methane, bis[2-[(4S)-methy1-5,5-di(3- methylphenyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5- di(4-methylphenyl)oxazoline]]methane, bis[2-[(4S)-methy1- 5,5-di(2-methoxyphenyl)oxazoline]]methane, bis[2-[(4S)- methy1-5,5-di(3-methoxyphenyl)oxazoline]]methane, bis[2- [(4S)-methy1-5,5-di(4-methoxyphenyl)oxazoline]]methane, bis[(4S)-methy1-5,5-dibenzyloxazoline]]methane, bis[2- [(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5-di(4-methylbenzyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5-di(2- methoxybenzyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5- di(3-methoxybenzyl)oxazoline]]methane, bis[2-[(4S)-methy1- 5,5-di(4-methoxybenzyl)oxazoline]]methane, bis[2- [spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]methane, bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclopentane]]]methane, bis[2-[spiro[(4S)-methyloxazoline- 5,1'-cyclohexane]]]methane, bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]methane, 2,2-bis[2-[(4S)-methyloxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-dimethyloxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-diethyloxazoline]Jpropane, 2,2-bis[2-[(4S)- methy1-5,5-di(n-propyl)oxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-diphenyloxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-di(3-methylphenyl)oxazoline]]propane, 2,2-bis[2- [(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]propane, 2,2- bis[2-[(4S)-methy1-5,5-di(2- methoxyphenyl)oxazoline]]propane, 2,2-bis[2-[(4S)-methy1- 5,5-di(3-methoxyphenyl)oxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-di(4-methoxyphenyl)oxazoline]]propane, 2,2- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]propane, 2,2- bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]propane, 2,2-bis[2-[(4S)-methy1-5, 5-di(4 - methylbenzyl)oxazoline]]propane, 2,2-bis[2-[(4S)-methy1- 5,5-di(2-methoxybenzyl)oxazoline]]propane, 2,2-bis[2-[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]propane, 2,2- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]propane, 2,2-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cyclobutane]]]propane, 2,2-bis[2- [spiro[(4S)-methyloxazoline-5,1'-cyclopentane]]]propane, 2,2-bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclohexane]]]propane, 2,2-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]propane, 3,3-bis[2-[(4S)-methyloxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-dimethyloxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-diethyloxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-di(n-propyl)oxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-diphenyloxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-di(3-methylphenyl)oxazoline]]pentane, 3,3-bis[2- [(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]pentane, 3,3- bis[2-[(4S)-methy1-5,5-di(2- methoxyphenyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-methy1- 5,5-di(3-methoxyphenyl)oxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-di(4-methoxyphenyl)oxazoline]]pentane, 3,3- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]pentane, 3,3- bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-methy1-5,5-di(4- methylbenzyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-methy1- 5,5-di(2-methoxybenzyl)oxazoline]]pentane, 3,3-bis[2-[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]pentane, 3,3- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]pentane, 3,3-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cyclobutane]]]pentane, 3,3-bis[2- [spiro[(4S)-methyloxazoline-5,l'-cyclopentane]]]pentane, 3,3-bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclohexane]]]pentane, 3,3-bis[2-[spirot(4S)- methyloxazoline-5,1'-cycloheptane]]]pentane, 4,4-bis[2-[(4S)-methyloxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-dimethyloxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-diethyloxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-di(n-propyl)oxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-diphenyloxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-di(3-methylphenyl)oxazoline]]heptane, 4,4-bis[2- [(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]heptane, 4,4- bis[2-[(4S)-methy1-5,5-di(2- methoxyphenyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-methy1- 5,5-di(3-methoxyphenyl)oxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-di(4-methoxyphenyl)oxazoline]]heptane, 4,4- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]heptane, 4,4- bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-methy1-5,5-di(4- methylbenzyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-methy1- 5,5-di(2-methoxybenzyl)oxazoline]]heptane, 4,4-bis[2-[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]heptane, 4,4- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]heptane, 4,4-bis[2-[spirof(4S)- methyloxazoline-5,1'-cyclobutane]]]heptane, 4,4-bis[2- [spirof(4S)-methyloxazoline-5,1'-cyclopentane]]]heptane, 4,4-bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclohexane]]]heptane, 4,4-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]heptane, l,1-bis[2-[(4S)-methyloxazoline]]cyclopropane, 1,1-bis[2- [(4S)-methy1-5,5-dimethyloxazoline]]cyclopropane, 1,1- bis[2-[(4S)-methy1-5,5-diethyloxazoline]]cyclopropane, 1,1- bis[2-[(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclopropane, l,1-bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclopropane, l,1-bis[2-[(4S)-methy1-5,5-di(3- methylphenyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylphenyl)oxazoline]]cyclopropane, 1,1- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclopropane, 1,1-bis[2-[(4S)-methy1-5,5-di(3- methylbenzyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclopropane, 1,1- bis[2-[(4S)-methy1-5,5-di(2- methoxybenzyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclopropane, 1,1- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]cyclopropane, 1,1-bis[2- [spirot(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclopropane, 1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclopentane]]]cyclopropane, 1,1-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]cyclopropane, l,1-bis[2-[(4S)-methyloxazoline]]cyclopropane, 1,1-bis[2- [(4S)-methy1-5,5-dimethyloxazoline]]cyclobutane, 1,1-bis[2- [(4S)-methy1-5,5-diethyloxazoline]]cyclobutane, 1,1-bis[2- [(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-di(3- methylphenyl)oxazoline]]cyclobutane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylphenyl)oxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-di(3- methylbenzyl)oxazoline]]cyclobutane, l,1-bis[2-[(4S)- methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-di(2- methoxybenzyl)oxazoline]]cyclobutane, 1,1-bis[2 -[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclobutane, 1,1- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]cyclobutane, 1,1-bis[2- [spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclobutane, 1,1-bis[2-[spirot(4S)-methyloxazoline-5,1'- cyclopentane]]]cyclobutane, 1,1-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]cyclobutane, 1,1-bis[2-[(4S)-methyloxazoline]]cyclopentane, 1,1-bis[2- [(4S)-methy1-5,5-dimethyloxazoline]]cyclopentane, 1,1- bis[2-t(4S)-methy1-5,5-diethyloxazoline]]cyclopentane, 1,1- bis[2-t(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclopentane, l,1-bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclopentane, l,1-bis[2-[(4S)-methy1-5,5-di(3- methylphenyl)oxazoline]]cyclopentane, 1,1-bis[2 -[(4S)- methy1-5,5-di(4-methylphenyl)oxazoline]]cyclopentane, 1,1- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclopentane, l,1-bis[2-[(4S)-methy1-5,5-di(3- methylbenzyl)oxazoline]]cyclopentane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclopentane, 1,1- bis[2-[(4S)-methy1-5,5-di(2- methoxybenzyl)oxazoline]]cyclopentane, 1,1-bis[2-[(4S)- methy1-5,5 -di(3-methoxybenzyl)oxazoline]]cyclopentane, 1,1- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]cyclopentane, 1,1-bis[2- [spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclopentane, 1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1' - cyclopentane]]]cyclopentane, 1,1-bis[2-[spiro[(4S)- methyloxazoline-5,1'-cycloheptane]]]cyclopentane, l,1-bis[2-[(4S)-methyloxazoline]]cyclohexane, 1,1-bis[2- [(4S)-methy1-5,5-dimethyloxazoline]]cyclohexane, 1,1-bis[2- [(4S)-methy1-5,5-diethyloxazoline]]cyclohexane, 1,1-bis[2- [(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-di(3- methylphenyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylphenyl)oxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-di(3- methylbenzyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)- methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-di(2- methoxybenzyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)- methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclohexane, 1,1- bis[2-[(4S)-methy1-5,5-di(4- methoxybenzyl)oxazoline]]cyclohexane, 1,1-bis[2- [spiro[(4S)-methyloxazoline-5,l'-cyclobutane]]]cyclohexane, 1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1'- cyclopentane]]]cyclohexane, 1,1-bis[2-[spiro f(4S)- methyloxazoline-5,1'-cycloheptane]]]cyclohexane; and these compounds in which methyl group at the 4-positon of the oxazoline ring is respectively replaced with an isopropyl, isobutyl, tert-butyl, benzyl, phenyl, 1-naphthyl or 2- naphthyl group. These compounds of which the configuration (4S) at the 4-positon of the oxazoline ring is changed to (4R) such as bis[2-[(4R)-methyloxazoline]]methane are also exemplified. Further, these compounds of which one configuration is (4S) and other is (4R) among two bisoxazoline skeletons such as 1-[2-[(4R)-methyloxazoline]-1-[2-[(4S)- methyloxazoline]]methane are also exemplified. These optically active bisoxazoline compounds (1) may be used alone, or two or more kinds thereof may be used. The optically active bisoxazoline compound (1) can be produced by a method comprising contacting an optically active diamide compound represented by the formula (8): wherein R1, R2, R3, R4 and R5 are the same as described above, which is obtained by reacting an optically active aminoalcohol compound represented by the formula (6): wherein R1, R2, and R3 are the same as described above, with a compound represented by the formula (7): wherein R4 and R5 are the same as described above and Z represents an alkoxy group or a halogen atom, with a Lewis acid, for example, as described in EP 895992 A. In the formula of the boron compound represented by the formula (2) (hereinafter, simply referred to as the boron compound (2)) which is the component (C), A represents a lithium atom, a sodium atom, a potassium atom, a silver atom or a trityl group and the trityl group is preferable. X represents a fluorine atom or a fluorine- substituted C1-C8 alkyl group and n represents an integer of 1 to 5. Examples of the fluorine-substituted C1-C8 alkyl group include a fluoromethyl, difluoromethyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl and perfluorooctyl group. Examples of the boron compound (2) include lithium tetrakis(4-fluorophenyl)borate, sodium tetrakis(4- fluorophenyl)borate, potassium tetrakis(4- fluorophenyl)borate, silver tetrakis(4-fluorophenyl)borate, trityl tetrakis(4-fluorophenyl)borate, lithium tetrakis(3,5-difluorophenyl)borate, sodium tetrakis(3,5- difluorophenyl)borate, potassium tetrakis(3,5- difluorophenyl)borate, silver tetrakis(3,5- difluorophenyl)borate, trityl tetrakis(3,5- difluorophenyl)borate, lithium tetrakis(3,4,5- trifluorophenyl)borate, sodium tetrakis(3,4,5- trifluorophenyl)borate, potassium tetrakis(3,4,5- trifluorophenyl)borate, silver tetrakis(3,4,5- trifluorophenyl)borate, trityl tetrakis(3,4,5- trifluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, lithium tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, sodium tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, potassium tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, silver tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, trityl tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, lithium tetrakis[2,4,6- tris(trifluoromethyl)phenyl]borate, sodium tetrakis[2,4,6- tris(trifluoromethyl)phenyl]borate, potassium tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, silver tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, trityl tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, lithium tetrakis[pentakis(trifluoromethyl)phenyl]borate, sodium tetrakis[pentakis(trifluoromethyl)phenyl]borate, potassium tetrakis[pentakis(trifluoromethyl)phenyl]borate, silver tetrakis[pentakis(trifluoromethyl)phenyl]borate and trityl tetrakis[pentakis(trifluoromethyl)phenyl]borate. In terms of handling easily, trityl tetrakis(4-fluorophenyl)borate, trityl tetrakis(3,5-difluorophenyl)borate, trityl tetrakis(3,4,5-trifluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, trityl tetrakis[3,5- bis(trifluoromethyl)phenyl]borate, trityl tetrakis[2,4,6- tris(trifluoromethyl)phenyl]borate and trityl tetrakis[pentakis(trifluoromethyl)phenyl]borate are preferable and trityl tetrakis(pentafluorophenyl)borate and trityl tetrakis[3,5-bis(trifluoromethyl)phenyl]borate are more preferable. As the boron compound (2) , a commercial available compound can be used as it is and the compound produced by a known method described in JP 9-295984 A and the like may be used. The boron compound (2) may be used alone, or two or more kinds thereof may be used. The amount of the component (B) to be used is usually 0.8 to 5 moles, preferable 0.9 to 2 moles relative to 1 mole of the component (A). The amount of the component (C) to be used is usually 0.8 to 5 moles, preferable 0.9 to 2 moles relative to 1 mole of the component (A). The asymmetric copper complex of the present invention can be obtained by mixing the component (A), the component (B) and the component (C). The mixing order is not particularly limited and for example, it is carried out by a method comprising mixing the component (A) and the component (B) in a solvent followed by adding the component (C) thereto and the like. The operation of mixing is usually carried out in the presence of a solvent. Examples of the solvent include a halogenated hydrocarbon solvent such as dichloromethane, 1,2-dichloroethane, chloroform and carbon tetrachloride, an aromatic hydrocarbon solvent such as toluene and xylene, and an ester solvent such as ethyl acetate. When the olefin represented by the formula (3) (hereinafter, simply referred to as the olefin (3)) described below is a liquid, the olefin (3) may be used as the solvent. The amount of the solvent to be used is usually 10 to 500 parts by weight relative to 1 part by weight of the copper compound. The operation of mixing is usually carried out in an atmosphere of an inert gas such as argon and nitrogen. The temperature of mixing is usually -20 to 100°C. The asymmetric copper complex can be isolated by concentrating a solution obtained by mixing the component (A), the component (B) and the component (C), and the solution obtained may be used for the reaction of the olefin (3) and the diazoacetic acid ester represented by the formula (4) (hereinafter, simply referred to as the diazoacetic acid ester (4)) described below without isolating the asymmetric copper complex. The optically active cyclopropanecarboxylate compound represented by the formula (5) (hereinafter, simply referred to as the optically active cyclopropane compound (5)) is obtained by reacting the olefin (3) with the diazoacetic acid ester (4) in the presence of the asymmetric copper complex thus obtained. In the formula of the olefin (3), R6, R7, R8 and R9 are the same or different, and independently represent a hydrogen atom; a halogen atom; a C1-C6 alkyl group which is optionally substituted with a halogen atom or atoms, a C1- C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2-C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C7-C11 aryloxycarbonyloxy group or groups; a C1-C6 alkenyl group which is optionally substituted with a halogen atom or atoms, or a C2-C7 alkoxycarbonyl group or groups; a C6-C10 aryl group which is optionally substituted with a C1-C6 alkoxy group or groups; a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups; or a C2-C7 alkoxycarbonyl group which is optionally substituted with a halogen atom or atoms, a C1-C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2- C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C7-C11 aryloxycarbonyloxy group or groups. Examples of the halogen atom include a fluorine, chlorine, bromine and iodine atom. Examples of the halogen atom and the C1-C6 alkoxy group of the C1-C6 alkyl group which is optionally substituted with the halogen atom or atoms, the C1-C6 alkoxy group or groups, the C7-C12 aralkyloxy group or groups, the C2-C10 acyloxy group or groups, the C2-C7 alkoxycarbonyloxy group or groups, or the C7-C11 aryloxycarbonyloxy group or groups are the same as those exemplified above. Examples of the C7-C12 aralkyloxy group include a benzyloxy, 4-methylbenzyloxy and (1- naphthyl)methoxy group. Examples of the C2-C10 acyloxy group include an acetoxy and benzoyloxy group. Examples of the C2-C7 alkoxycarbonyloxy group include a methoxycarbonyloxy, ethoxycarbonyloxy and tert- butoxycarbonyloxy group. Examples of the C7-C11 aryloxycarbonyloxy group include a phenoxycarbonyloxy group. Examples of the C1-C6 alkyl group which is optionally substituted with the halogen atom or atoms, the C1-C6 alkoxy group or groups, the C7-C12 aralkyloxy group or groups, the C2-C10 acyloxy group or groups, the C2-C7 alkoxycarbonyloxy group or groups, or the C7-C11 aryloxycarbonyloxy group or groups include a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, chloromethyl, fluoromethyl, trifluoromethyl, chloroethyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, tert-butoxymethyl, benzyloxymethyl, acetoxymethyl, benzoylmoxymethyl, methoxycarbonyloxymethyl, ethoxucarbonyloxymethyl, tert- butoxycarbonyloxymethyl and phenoxycarbonyloxymethyl group. Examples of the C1-C6 alkenyl group which is optioanlly substituted with the halogen atom or atoms or the C2-C7 alkoxycarbonyl group or groups include an ethenyl, 1-propenyl, 2-propenyl, 2-methy1-propenyl, 1-butenyl, 2- butenyl, 3-butenyl, 1-chloro-2-propenyl and 2- methoxycarbony1-1-propenyl group. Examples of the C6-C10 aryl group which is optionally substituted with the C1-C6 alkoxy group or groups include a phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 4- methylphenyl, 3-(methoxymethyl)phenyl and 2,3- dihydrobenzofuran-4-yl group. Examples of the C7-C12 aralkyl group which is optionally substituted with the C1-C6 alkoxy group or groups include a benzyl, 2-methylbenzyl, 3-methylbenzyl, 4- methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4- methoxybenzyl, (1-naphthyl)methyl and (2-naphthyl)methyl group. Examples of the C2-C7 alkoxycarbonyl group which is optionally substituted with the halogen atom or atoms, the C1-C6 alkoxy group or groups, the C7-C12 aralkyloxy group or groups, the C2-C10 acyloxy group or groups, the C2-C7 alkoxycarbonyloxy group or groups, or the C7-C11 aryloxycarbonyloxy group or groups include a methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl and n-pentyloxycarbonyl group. When R6 and R8 represent the same in the formula of the olefin (3), R6 and R7 represent different groups each other. Examples of the olefin (3) include propene, fluoroethylene, 1-fluoro-1-chloroethylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 4-chloro-1-butene, 2-pentene, 2-heptene, 2-methy1-2-butene, 2,5-dimethy1-2,4- hexadiene, 2-chloro-5-methy1-2,4-hexadiene, 2-fluoro-5- methy1-2,4-hexadiene, 1,1,1-trifluoro-5-methy1-2,4- hexadiene, 2-methoxycarbony1-5-methy1-2,4-hexadiene, 1,1- difluoro-4-methy1-l,3-pentadiene, 1,1-dichloro-4-methy1- 1,3-pentadiene, 1,1-dibromo-4-methy1-l,3-pentadiene, 1- chloro-1-fluoro-4-methy1-1,3-pentadiene, 1-fluoro-1-bromo- 4-methy1-l,3-pentadiene, 2-methy1-2,4-hexadiene, 1-fluro- 1,1-dichloro-4-methy1-2-pentene, 1,1,1-trichloro-4-methy1- 3-pentene, 1,1,1-tribromo-4-methy1-3-pentene, 2,3-dimethy1- 2-pentene, 2-methy1-3-pheny1-2-butene, 2-bromo-2,5- dimethy1-4-hexene, 2-chloro-2,5-dimethy1-4-hexene, 1- chloro-2,5-dimethy1-2,4-hexadiene, (3-methy1-2-butenyl) methyl ether, (3-methy1-2-butenyl) tert-butyl ether, (3- methy1-2-butenyl) benzyl ether, 3-methy1-2-butenyl acetate, 3-methy1-2-butenyl benzoate, (3-methy1-2-butenyl) methyl carbonate, (3-methy1-2-butenyl) tert-butyl carbonate, (3- methy1-2-butenyl) phenyl carbonate, styrene and 4-viny1- 2,3-dihydrobenzofuran. In the formula of the diazoacetic acid ester (4), R10 represents a C1-C6 alkyl group. Examples of the alkyl group include a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and n-pentyl group. Examples of the diazoacetic acid ester (4) include methyl diazoacetate, ethyl diazoacetate, n-propyl diazoacetate, isopropyl diazoacetate, n-butyl diazoacetate, isobutyl diazoacetate and tert-butyl diazoacetate. As the diazoacetic acid ester (4), those produced by a known method such as Organic Synthesis Collective Volume 3, p.392 can be used. The amount of the asymmetric copper complex to be used is usually 0.00001 to 0.5 mole, preferably in the range of about 0.0001 to 0.05 mole in terms of the copper metal relative to 1 mole of the diazoacetic acid ester (4). The amount of the olefin (3) to be used is usually 1 mole or more, preferably 1.2 moles or more relative to 1 mole of the diazoacetic acid ester (4). There is no specific upper limit and, when the olefin (3) is a liquid, excess amount thereof, for example, about 100 moles relative 1 mole of the diazoacetic acid ester (4), may be used as the solvent. The reaction of the olefin (3) and the diazoacetic acid ester (4) is usually carried out in an atmosphere of an inert gas such as argon and nitrogen. Since water adversely affects the reaction, the reaction is preferably carried out with suppressing the amount of water present in the reaction system. As a method for suppressing the amount of water present in the reaction system, method comprising making a dehydrating agent such as molecular sieves, magnesium sulfate and sodium sulfate anhydride coexist in the reaction system, and using the olefin (3) or the solvent previously subjected to dehydration treatment. The reaction temperature is usually about -50 to 150°C, preferably about -20 to 80°C. The reaction of the olefin (3) and the diazoacetic acid ester (4) is usually carried out by mixing the asymmetric copper complex, the olefin (3) and the diazoacetic acid ester (4), and if necessary, in the presence of a solvent. The mixing order is not particularly limited. Usually, the asymmetric copper complex and the olefin (3) are mixed in the solvent and then the diazoacetic acid ester (4) is added thereto. Examples of the solvent include a halogenated hydrocarbon solvent such as dichloromethane, 1,2- dichloroethane, chloroform and carbon tetrachloride, an aliphatic hydrocarbon solvent such as hexane, heptane and cyclohexane, an aromatic hydrocarbon solvent such as toluene and xylene, and an ester solvent such as ethyl acetate. They can be used alone or in the form of a mixed solvent. As described above, when the olefin (3) is a liquid, the olefin (3) may also be used as the solvent. When the solvent is used, the amount of the solvent to be used is not particularly limited, and in viewpoint of the volume efficiency and the properties of the reaction mixture, the amount thereof is usually about 2 to 30 parts by weight, preferably about 4 to 20 parts by weight relative to 1 part by weight of the diazoacetic acid ester (4). When the asymmetric copper complex prepared using the divalent copper compound as the component (A) is used, a reducing agent such as phenylhydrazine may be used together. After completion of the reaction, the optically active cyclopropane compound (5) can be isolated by, for example, distilling the reaction mixture. The optically active cyclopropane compound (5) isolated may be further purified, if necessary, by a conventional purification means such as column chromatography. Examples of the optically active cyclopropane compound (5) include optically active methyl 2- fluorocyclopropanecarboxylate, optically active methyl 2- fluoro-2-chlorocyclopropanecarboxylate, optically active methyl 2-methylcyclopropanecarboxylate, optically active methyl 2,2-dimethylcyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-methy1-1- propenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2,2-dichloroethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2,2,2- trichloroethyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2,2,2- tribromoethyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2,2- dibromoethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2, 2- difluoroethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-fluoro-2- chloroethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-fluoro-2- bromoethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-fluoro-1- propenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-chloro-1-propenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-chloro-2- trifluoromethylethenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-methoxycarbony1-1- propenyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-chloro-2- methylpropyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(2-bromo-2- methylpropyl)cyclopropanecarboxylate, optically active methyl 2,2-dimethy1-3-(1-propenyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (methoxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2-(tert- butoxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (benzyloxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (benzoyloxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (methoxycarbonyloxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2-(tert- butoxycarbonyloxymethyl)cyclopropanecarboxylate, optically active methyl 3,3-dimethy1-2- (phenoxycarbonyloxymethyl)cyclopropanecarboxylate, optically active methyl 2-phenylcyclopropanecarboxylate and optically active methyl 2-(2,S-dihydrobenzofuran^- ylJcyclopropanecarboxylate; and compounds wherein the above methyl ester moieties are replaced with ethyl, n-propyl, isopropyl, isobutyl or tert-butyl ester moieties. Examples In the following Examples, the yield was calculated based on the diazoacetic acid ester by the gas chromatography internal standard method. The trans- isomer/cis-isomer ratio was calculated based on the area ratio of the gas chromatography. The optically purity was calculated based on the area ratio of the liquid chromatography. The trans-isomer means the compound having the ester group at 1-position and the substituent at 2- position on the opposite side with respect to the cyclopropane ring plane and the cis-isomer means the compound having the ester group at 1-position and the substituent at 2-position on the same side. Example 1 Into a 50 ml Schlenk tube purged with nitrogen, 1.98 mg of copper(I) chloride, 6.43 mg of 1,1-bis[2-[(4S)-(tert- butyl)oxazoline]]cyclopropane and 5 ml of 1,2- dichloroethane were charged. To the pale yellow mixture obtained by mixing them, 20.29 mg of trityl tetrakis(penntafluorophenyl)borate was added and the resulting mixture was stirred at room temperature for 10 minutes to obtain the yellow homogeneous solution containing the asymmetric copper complex. The ultraviolet absorption spectrum of the solution was measured to confirm the generation of new peaks at 290 nm, 350 nm, and 740 nm. The solution was analyzed by gas chromatography to confirm the production of trityl chloride. After 10.25 g of 3-methy1-2-butenyl acetate was added to the homogeneous solution containing the asymmetric copper complex obtained and the inner temperature was adjusted to 20°C, 5 ml of the 1,2-dichloroethane solution containing ethyl diazoacetate (concentration: 4 mol/1) was added dropwise thereto over 4 hours and the resulting mixture was reacted at the same temperature for 30 minutes to obtain the solution containing ethyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate. Yield: 80% Trans-isomer/cis-isomer ratio: 89/11 Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis- isomer 5%e.e. ((-)-isomer) Example 2 According to the same manner as that described in Example 1, the solution containing ethyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate was obtained except that 24.32 mg of trityl tetrakis[3,5- bis(trifluoromethyl)phenyl]borate was used in place of 20.29 mg of trityl tetrakis(pentafluorophenyl)borate. Yield: 81% Trans-isomer/cis-isomer ratio: 88/12 Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis- isomer 9%e.e. ((+)-isomer) Example 3 According to the same manner as that described in Example 1, the solution containing ethyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate was obtained except that 2.69 mg of copper(II) chloride was used in place of 1.98 mg of copper(I) chloride. Yield: 78% Trans-isomer/cis-isomer ratio: 89/11 Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis- isomer 4%e.e. ((-)-isomer) Comparative Example 1 Into a 50 ml Schlenk tube purged with nitrogen, 5.17 mg of copper(I) trifluoromethanesulfonate toluene complex, 6.43 mg of 1,1-bis[2-[(4S)-(tert- butyl)oxazoline]]cyclopropane and 5 ml of 1,2- dichloroethane were charged and the resulting mixture was stirred at room temperature for 10 minutes to obtain the yellow homogeneous solution containing the asymmetric copper complex. After 10.25 g of 3-methy1-2-butenyl acetate was added thereto and the inner temperature was adjusted to 20°C, 5 ml of the 1,2-dichloroethane solution containing ethyl diazoacetate (concentration: 4 mol/1) was added dropwise thereto over 4 hours and the resulting mixture was reacted at the same temperature for 30 minutes to obtain the solution containing ethyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate. Yield: 60% Trans-isomer/cis-isomer ratio: 81/19 Optically purity: trans-isomer 92%e.e. ((+)-isomer), cis- isomer 65%e.e. ((+)-isomer) Example 4 According to the same manner as that described in Example 1, the solution containing ethyl 3,3-dimethy1-2- (benzyloxymethyl)cyclopropanecarboxylate was obtained except that 7.08 g of (3-methy1-2-butenyl) benzyl ether was used in place of 10.25 g of 3-methy1-2-butenyl acetate. Yield: 89% Trans-isomer/cis-isomer ratio: 92/8 Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis- isomer 3%e.e. ((-)-isomer) Comparative Example 2 According to the same manner as that described in Comparative Example 1, the solution containing ethyl 3,3- dimethy1-2-(benzyloxymethyl)cyclopropanecarboxylate was obtained except that 7.08 g of (3-methy1-2-butenyl) benzyl ether was used in place of 10.25 g of 3-methy1-2-butenyl acetate. Yield: 71% Trans-isomer/cis-isomer ratio: 84/16 Optically purity: trans-isomer 88%e.e. ((+)-isomer), cis- isomer 52%e.e. ((-)-isomer) Example 5 According to the same manner as that described in Example 1, the solution containing ethyl 3,3-dimethy1-2- (acetoxymethyl)cyclopropanecarboxylate was obtained except that the amount of 3-methy1-2-butenyl acetate to be used was 20.50 g and the amount of the 1,2-dichloroethane solution containing ethyl diazoacetate (concentration: 4 mol/1) to be used was 10 ml. Yield: 74% Trans-isomer/cis-isomer ratio: 86/14 Optically purity: trans-isomer 93%e.e. ((+)-isomer), cis- isomer 12%e.e. ((-)-isomer) Comparative Example 3 According to the same manner as that described in Comparative Example 1, the solution containing ethyl 3,3- dimethy1-2-(acetoxymethyl)cyclopropanecarboxylate was obtained except that the amount of 3-methy1-2-butenyl acetate to be used was 20.50 g and the amount of the 1,2- dichloroethane solution containing ethyl diazoacetate (concentration: 4 mol/1) to be used was 10 ml. Yield: 43% Trans-isomer/cis-isomer ratio: 80/20 Optically purity: trans-isomer 93%e.e. ((+)-isomer), cis- isomer 61%e.e. ((-)-isomer) Industrial Applicability According to the process of the present invention, an optically active cyclopropanecarboxylate compound, which is useful as a synthetic intermediate of pesticides and pharmaceuticals such as synthesized pyrethroid insecticides, can be obtained. 1. An asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound, (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 are the same or different, and independently represent a hydrogen atom; a C1-C6 alkyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups, or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups, or R1 and R2 are bonded together to represent a C2-C6 polymethylene group, R3 represents a methyl group; an isopropyl group; an isobutyl group; a tert-butyl group; a 1-naphthyl group; a 2-naphthyl group; a phenyl group which is optionally substituted with a C1-C6 alkyl group or groups, or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups, and R4 and R5 are the same and represent hydrogen atoms or C1- C3 alkyl groups, or R4 and R5 are bonded together to represent a C2-C5 polymethylene group, and (C) at least one boron compound represented by the formula (2): wherein A represents a lithium atom, a sodium atom, a potassium atom, a silver atom or a trityl group, X represents a fluorine atom or a fluorine-substituted C1-C8 alkyl group, and n represents an integer of 1 to 5. 2. The asymmetric copper complex according to claim 1, wherein the component (A) is at least one monovalent copper compound. 3. The asymmetric copper complex according to claim 1, wherein the copper compound is a copper halide in the component (A). 4. The asymmetric copper complex according to claim 1, wherein A is the trityl group in the component (C). 5. A process for production of an optically active cyclopropanecarboxylate compound represented by the formula wherein R6, R7, R8 and R9 are the same or different, and independently represent a hydrogen atom; a halogen atom; a C1-C6 alkyl group which is optionally substituted with a halogen atom or atoms, a C1-C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2-C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C6-C10 aryloxycarbonyloxy group or groups; a C1-C6 alkenyl group which is optionally substituted with a halogen atom or atoms or a C2-C7 alkoxycarbonyl group or groups; a C6- C10 aryl group which is optionally substituted with a C1-C6 alkoxy group or groups; a C7-C12 aralkyl group which is optionally substituted with a C1-C6 alkoxy group or groups; or a C2-C7 alkoxycarbonyl group which is optionally substituted with a halogen atom or atoms, a C1-C6 alkoxy group or groups, a C7-C12 aralkyloxy group or groups, a C2- C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a C6-C10 aryloxycarbonyloxy group or groups; provided that, when R6 and R8 represent the same, R6 and R7 represent different groups each other; and R10 represents a C1-C6 alkyl group. which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): wherein R10 is as described above, in the presence of the asymmetric copper complex described in claim 1. 6. The process according to claim 5, wherein in the formula (3), (a) R6 and R8 are methyl groups, R7 is a hydrogen atom; a C1-C6 alkyl group substituted with a C7-C12 aralkyloxy group or groups, or a C2-C10 acyloxy group or groups; or a C1-C6 alkenyl group which is optionally substituted with a halogen atom or atoms, and R9 is a hydrogen atom or (b) R6 and R8 are hydrogen atoms, R7 is an aryl group which is optionally substituted with a C1-C6 alkoxy group or groups; or a halogen atom, and R9 is a hydrogen or halogen atom. 7. The process according to claim 5, wherein in the formula (3), (a) R6 and R8 are methyl groups, R7 is a hydrogen atom, a benzyloxymethyl group, an acetoxymethyl group, a 2-methy1- 1-propenyl group, a 2,2-dichloroethenyl group, a 2.2- dibromoethenyl group or 2-chloro-2-fluoroethenyl group, and R9 is a hydrogen atom or (b) R6 and R8 are hydrogen atoms, R7 is a 2,3- dihydrobenzofuran-4-yl group or a fluorine atom, and R9 is a hydrogen or fluorine atom. A process for production of an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or the like and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): wherein R10 is as described above, in the presence of an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound. (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 represent a C1-C6 alkyl group or the like; R3 represents a tert-butyl group or the like; and R4 and R5 are the same and represent C1-C3 alkyl groups or the like, and (C) at least one boron compound represented by the formula (2): wherein A represents a trityl group or the like, X represents a fluorine atom or the like, and n represents an integer of 1 to 5.

Full Text

DESCRIPTION
PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE
CYCLOPROPANECARBOXYLATE COMPOUND
Technical Field
The present invention relates to a process for
production of an optically active cyclopropanecarboxylate
compound.
Background Art
Optically active cyclopropanecarboxylate compounds
whose representative examples are (+)-trans-2,2-dimethy1-3-
(2-methy1-1-propenyl)cyclopropanecarboxylate and (+)-trans-
3,3-dimethy1-2-(acetoxymethyl)cyclopropanecarboxylate are
important compounds as synthetic intermediates of
pesticides and pharmaceuticals such as synthesized
pyrethroid insecticides and methods for producing it are
described in EP 895992 A, US 6858559, Tetrahedron Lett., 32,
7373 (1991), Tetrahedron, 57, 6083 (2001) and the like.
Disclosure of the Invention
The present invention provides an asymmetric copper
complex obtained by mixing
(A) at least one monovalent or divalent copper

compound,
(B) at least one optically active bisoxazoline
compound represented by the formula (1):

wherein R1 and R2 are the same or different, and
independently represent a hydrogen atom; a C1-C6 alkyl
group; a phenyl group which is optionally substituted with
a C1-C6 alkyl group or groups or a C1-C6 alkoxy group or
groups; or a C7-C12 aralkyl group which is optionally
substituted with a C1-C6 alkoxy group or groups, or R1 and
R2 are bonded together to represent a C2-C6 polymethylene
group,
R3 represents a methyl group; an isopropyl group; an
isobutyl group; a tert-butyl group; a 1-naphthyl group; a
2-naphthyl group; a phenyl group which is optionally
substituted with a C1-C6 alkyl group or groups or a C1-C6
alkoxy group or groups; or a C7-C12 aralkyl group which is
optionally substituted with a C1-C6 alkoxy group or groups,
and
R4 and R5 are the same and represent hydrogen atoms or C1-
C3 alkyl groups, or R4 and R5 are bonded together to

represent a C2-C5 polymethylene group, and
(C) at least one boron compound represented by the
formula (2):

wherein A represents a lithium atom, a sodium atom, a
potassium atom, a silver atom or a trityl group, X
represents a fluorine atom or a fluorine-substituted C1-C8
alkyl group, and X represents an integer of 1 to 5, and a
process for production of an optically active
cyclopropanecarboxylate compound represented by the formula
(5):

wherein R6, R7, R8 and R9 are the same or different, and
independently represent a hydrogen atom; a halogen atom; a
C1-C6 alkyl group which is optionally substituted with a
halogen atom or atoms, a C1-C6 alkoxy group or groups, a
C7-C12 aralkyloxy group or groups, a C2-C10 acyloxy group
or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a
C6-C10 aryloxycarbonyloxy group or groups; a C1-C6 alkenyl

group which is optionally substituted with a halogen atom
or atoms or a C2-C7 alkoxycarbonyl group or groups; a C6-
C10 aryl group which is optionally substituted with a C1-C6
alkoxy group or groups; a C7-C12 aralkyl group which is
optionally substituted with a C1-C6 alkoxy group or groups;
or a C2-C7 alkoxycarbonyl group which is optionally
substituted with a halogen atom or atoms, a C1-C6 alkoxy
group or groups, a C7-C12 aralkyloxy group or groups, a C2-
C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy
group or groups, or a C6-C10 aryloxycarbonyloxy group or
groups; provided that, when R6 and R8 represent the same, R6

and R7 represent different groups each other; and R10
represents a C1-C6 alkyl group,
which comprises reacting an olefin represented by the
formula (3):

wherein R6, R7, R8 and R9 are as described above,
with a diazoacetic acid ester represented by the formula
(4):

wherein R10 is as described above, in the presence of the
asymmetric copper complex.

Best Mode for Carrying Out the Present Invention
Examples of the monovalent or divalent copper compound
which is component (A) include copper(I)
trifluoromethanesulfonate, copper(I) acetate, copper(I)
bromide, copper(I) chloride, copper(I) iodide, copper(I)
hydroxide, copper(II) trifluoromethanesulfonate, copper(II)
acetate, copper(II) bromide, copper(II) chloride,
copper(II) iodide and copper(II) hydroxide and the
monovalent copper compound is preferable. A copper halide
compound such as copper(I) chloride, copper(I) bromide,
copper(I) iodide, copper(II) chloride, copper(II) bromide
and copper(II) iodide is preferable. These copper
compounds may be used alone, or two or more kinds thereof
may be used.
As the monovalent or divalent copper compound, a
commercially available compound can be used as it is. A
monovalent copper compound prepared by contacting the
divalent copper compound with a reducing agent such as
phenylhydrazine may be used. A monovalent copper compound
may be generated to use by contacting the divalent copper
compound with a reducing agent such as phenylhydrazine in
the reaction system.
In the formula of the optically active bisoxazoline
compound represented by the formula (1) (hereinafter,
simply referred to as the optically active bisoxazoline

compound (1)) which is the component (B) , R1 and R2 are the
same or different, and independently represent a hydrogen
atom; a C1-C6 alkyl group; a phenyl group which is
optionally substituted with a C1-C6 alkyl group or groups
or a C1-C6 alkoxy group or groups; or a C7-C12 aralkyl
group which is optionally substituted with a C1-C6 alkoxy
group or groups, or R1 and R2 are bonded together to
represent a C2-C6 polymethylene group.
Examples of the C1-C6 alkyl group include a straight
or branched chain alkyl group such as a methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and n-hexyl
group.
Examples of the C1-C6 alkoxy group include a straight
or branched chain alkoxy group such as a methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy,
and n-hexyloxy group.
Examples of the phenyl group which is optionally
substituted with the C1-C6 alkyl group or groups or the C1-
C6 alkoxy group or groups include a phenyl, 3-methylphenyl,
4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl and 4-
methoxyphenyl group.
Examples of the C7-C12 aralkyl group which is
optionally substituted with the C1-C6 alkoxy group or
groups include a benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-
methylbenzyl, (1-naphthyl)methyl, (2-naphthyl)methyl, 2-

methoxybenzyl, 3-methoxylbenzyl and 4-methoxybenzyl group.
When R1 and R2 are bonded together to represent the
C2-C6 polymethylene group, examples of the C2-C6
polymethylene group include an ethylene, trimethylene,
tetramethylene, pentamethylene and hexamethylene group.
R3 represents a methyl group; an isopropyl group; an
isobutyl group; a tert-butyl group; a 1-naphthyl group; a
2-naphthyl group; a phenyl group which is optionally
substituted with a C1-C6 alkyl group or groups, or a C1-C6
alkoxy group or groups; or a C7-C12 aralkyl group which is
optionally substituted with a C1-C6 alkoxy group or groups.
Examples of the phenyl group which is optionally
substituted with the C1-C6 alkyl group or groups, or the
C1-C6 alkoxy group or groups and the C7-C12 aralkyl group
which is optionally substituted with the C1-C6 alkoxy group
or groups include the same groups as those exemplified
above.
R4 and R5 are the same and represent hydrogen atoms or
C1-C3 alkyl groups, or R4 and R5 are bonded together to
represent a C2-C5 polymethylene group.
Examples of the C1-C3 alkyl group include a methyl,
ethyl, n-propyl and isopropyl group. When R4 and R5 are
bonded together to represent the C2-C5 polymethylene group,
examples of the C2-C5 polymethylene group include an
ethylene, trimethylene, tetramethylene and pentamethylene

group.
Examples of the optically active bisoxazoline compound
(1) include bis[2-[(4S)-methyloxazoline]]methane, bis[2-
t(4S)-methy1-5,5-dimethyloxazoline]]methane, bis[2-[(4S)-
methy1-5,5-diethyloxazoline]]methane, bis[2-[(4S)-methy1-
5,5-di(n-propyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5-
diphenyloxazoline]]methane, bis[2-[(4S)-methy1-5,5-di(3-
methylphenyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5-
di(4-methylphenyl)oxazoline]]methane, bis[2-[(4S)-methy1-
5,5-di(2-methoxyphenyl)oxazoline]]methane, bis[2-[(4S)-
methy1-5,5-di(3-methoxyphenyl)oxazoline]]methane, bis[2-
[(4S)-methy1-5,5-di(4-methoxyphenyl)oxazoline]]methane,
bis[(4S)-methy1-5,5-dibenzyloxazoline]]methane, bis[2-
[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]methane,
bis[2-[(4S)-methy1-5,5-di(4-methylbenzyl)oxazoline]]methane,
bis[2-[(4S)-methy1-5,5-di(2-
methoxybenzyl)oxazoline]]methane, bis[2-[(4S)-methy1-5,5-
di(3-methoxybenzyl)oxazoline]]methane, bis[2-[(4S)-methy1-
5,5-di(4-methoxybenzyl)oxazoline]]methane, bis[2-
[spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]methane,
bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclopentane]]]methane, bis[2-[spiro[(4S)-methyloxazoline-
5,1'-cyclohexane]]]methane, bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]methane,
2,2-bis[2-[(4S)-methyloxazoline]]propane, 2,2-bis[2-[(4S)-

methy1-5,5-dimethyloxazoline]]propane, 2,2-bis[2-[(4S)-
methy1-5,5-diethyloxazoline]Jpropane, 2,2-bis[2-[(4S)-
methy1-5,5-di(n-propyl)oxazoline]]propane, 2,2-bis[2-[(4S)-
methy1-5,5-diphenyloxazoline]]propane, 2,2-bis[2-[(4S)-
methy1-5,5-di(3-methylphenyl)oxazoline]]propane, 2,2-bis[2-
[(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]propane, 2,2-
bis[2-[(4S)-methy1-5,5-di(2-
methoxyphenyl)oxazoline]]propane, 2,2-bis[2-[(4S)-methy1-
5,5-di(3-methoxyphenyl)oxazoline]]propane, 2,2-bis[2-[(4S)-
methy1-5,5-di(4-methoxyphenyl)oxazoline]]propane, 2,2-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]propane, 2,2-
bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]propane,
2,2-bis[2-[(4S)-methy1-5, 5-di(4 -
methylbenzyl)oxazoline]]propane, 2,2-bis[2-[(4S)-methy1-
5,5-di(2-methoxybenzyl)oxazoline]]propane, 2,2-bis[2-[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]propane, 2,2-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]propane, 2,2-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cyclobutane]]]propane, 2,2-bis[2-
[spiro[(4S)-methyloxazoline-5,1'-cyclopentane]]]propane,
2,2-bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclohexane]]]propane, 2,2-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]propane,
3,3-bis[2-[(4S)-methyloxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-dimethyloxazoline]]pentane, 3,3-bis[2-[(4S)-

methy1-5,5-diethyloxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-di(n-propyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-diphenyloxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-di(3-methylphenyl)oxazoline]]pentane, 3,3-bis[2-
[(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]pentane, 3,3-
bis[2-[(4S)-methy1-5,5-di(2-
methoxyphenyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-methy1-
5,5-di(3-methoxyphenyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-di(4-methoxyphenyl)oxazoline]]pentane, 3,3-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]pentane, 3,3-
bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]pentane,
3,3-bis[2-[(4S)-methy1-5,5-di(4-
methylbenzyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-methy1-
5,5-di(2-methoxybenzyl)oxazoline]]pentane, 3,3-bis[2-[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]pentane, 3,3-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]pentane, 3,3-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cyclobutane]]]pentane, 3,3-bis[2-
[spiro[(4S)-methyloxazoline-5,l'-cyclopentane]]]pentane,
3,3-bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclohexane]]]pentane, 3,3-bis[2-[spirot(4S)-
methyloxazoline-5,1'-cycloheptane]]]pentane,
4,4-bis[2-[(4S)-methyloxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-dimethyloxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-diethyloxazoline]]heptane, 4,4-bis[2-[(4S)-

methy1-5,5-di(n-propyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-diphenyloxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-di(3-methylphenyl)oxazoline]]heptane, 4,4-bis[2-
[(4S)-methy1-5,5-di(4-methylphenyl)oxazoline]]heptane, 4,4-
bis[2-[(4S)-methy1-5,5-di(2-
methoxyphenyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-methy1-
5,5-di(3-methoxyphenyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-di(4-methoxyphenyl)oxazoline]]heptane, 4,4-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]heptane, 4,4-
bis[2-[(4S)-methy1-5,5-di(3-methylbenzyl)oxazoline]]heptane,
4,4-bis[2-[(4S)-methy1-5,5-di(4-
methylbenzyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-methy1-
5,5-di(2-methoxybenzyl)oxazoline]]heptane, 4,4-bis[2-[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]heptane, 4,4-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]heptane, 4,4-bis[2-[spirof(4S)-
methyloxazoline-5,1'-cyclobutane]]]heptane, 4,4-bis[2-
[spirof(4S)-methyloxazoline-5,1'-cyclopentane]]]heptane,
4,4-bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclohexane]]]heptane, 4,4-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]heptane,
l,1-bis[2-[(4S)-methyloxazoline]]cyclopropane, 1,1-bis[2-
[(4S)-methy1-5,5-dimethyloxazoline]]cyclopropane, 1,1-
bis[2-[(4S)-methy1-5,5-diethyloxazoline]]cyclopropane, 1,1-
bis[2-[(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclopropane,

l,1-bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclopropane,
l,1-bis[2-[(4S)-methy1-5,5-di(3-
methylphenyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylphenyl)oxazoline]]cyclopropane, 1,1-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclopropane,
1,1-bis[2-[(4S)-methy1-5,5-di(3-
methylbenzyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclopropane, 1,1-
bis[2-[(4S)-methy1-5,5-di(2-
methoxybenzyl)oxazoline]]cyclopropane, 1,1-bis[2-[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclopropane, 1,1-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]cyclopropane, 1,1-bis[2-
[spirot(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclopropane,
1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclopentane]]]cyclopropane, 1,1-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]cyclopropane,
l,1-bis[2-[(4S)-methyloxazoline]]cyclopropane, 1,1-bis[2-
[(4S)-methy1-5,5-dimethyloxazoline]]cyclobutane, 1,1-bis[2-
[(4S)-methy1-5,5-diethyloxazoline]]cyclobutane, 1,1-bis[2-
[(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclobutane, 1,1-
bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclobutane, 1,1-
bis[2-[(4S)-methy1-5,5-di(3-
methylphenyl)oxazoline]]cyclobutane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylphenyl)oxazoline]]cyclobutane, 1,1-

bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclobutane, 1,1-
bis[2-[(4S)-methy1-5,5-di(3-
methylbenzyl)oxazoline]]cyclobutane, l,1-bis[2-[(4S)-
methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclobutane, 1,1-
bis[2-[(4S)-methy1-5,5-di(2-
methoxybenzyl)oxazoline]]cyclobutane, 1,1-bis[2 -[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclobutane, 1,1-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]cyclobutane, 1,1-bis[2-
[spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclobutane,
1,1-bis[2-[spirot(4S)-methyloxazoline-5,1'-
cyclopentane]]]cyclobutane, 1,1-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]cyclobutane,
1,1-bis[2-[(4S)-methyloxazoline]]cyclopentane, 1,1-bis[2-
[(4S)-methy1-5,5-dimethyloxazoline]]cyclopentane, 1,1-
bis[2-t(4S)-methy1-5,5-diethyloxazoline]]cyclopentane, 1,1-
bis[2-t(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclopentane,
l,1-bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclopentane,
l,1-bis[2-[(4S)-methy1-5,5-di(3-
methylphenyl)oxazoline]]cyclopentane, 1,1-bis[2 -[(4S)-
methy1-5,5-di(4-methylphenyl)oxazoline]]cyclopentane, 1,1-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclopentane,
l,1-bis[2-[(4S)-methy1-5,5-di(3-
methylbenzyl)oxazoline]]cyclopentane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclopentane, 1,1-

bis[2-[(4S)-methy1-5,5-di(2-
methoxybenzyl)oxazoline]]cyclopentane, 1,1-bis[2-[(4S)-
methy1-5,5 -di(3-methoxybenzyl)oxazoline]]cyclopentane, 1,1-
bis[2-[(4S)-methy1-5,5-di(4-
methoxybenzyl)oxazoline]]cyclopentane, 1,1-bis[2-
[spiro[(4S)-methyloxazoline-5,1'-cyclobutane]]]cyclopentane,
1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1' -
cyclopentane]]]cyclopentane, 1,1-bis[2-[spiro[(4S)-
methyloxazoline-5,1'-cycloheptane]]]cyclopentane,
l,1-bis[2-[(4S)-methyloxazoline]]cyclohexane, 1,1-bis[2-
[(4S)-methy1-5,5-dimethyloxazoline]]cyclohexane, 1,1-bis[2-
[(4S)-methy1-5,5-diethyloxazoline]]cyclohexane, 1,1-bis[2-
[(4S)-methy1-5,5-di(n-propyl)oxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-diphenyloxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-di(3-
methylphenyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylphenyl)oxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-dibenzyloxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-di(3-
methylbenzyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)-
methy1-5,5-di(4-methylbenzyl)oxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-di(2-
methoxybenzyl)oxazoline]]cyclohexane, 1,1-bis[2-[(4S)-
methy1-5,5-di(3-methoxybenzyl)oxazoline]]cyclohexane, 1,1-
bis[2-[(4S)-methy1-5,5-di(4-

methoxybenzyl)oxazoline]]cyclohexane, 1,1-bis[2-
[spiro[(4S)-methyloxazoline-5,l'-cyclobutane]]]cyclohexane,
1,1-bis[2-[spiro[(4S)-methyloxazoline-5,1'-
cyclopentane]]]cyclohexane, 1,1-bis[2-[spiro f(4S)-
methyloxazoline-5,1'-cycloheptane]]]cyclohexane; and these
compounds in which methyl group at the 4-positon of the
oxazoline ring is respectively replaced with an isopropyl,
isobutyl, tert-butyl, benzyl, phenyl, 1-naphthyl or 2-
naphthyl group. These compounds of which the configuration
(4S) at the 4-positon of the oxazoline ring is changed to
(4R) such as bis[2-[(4R)-methyloxazoline]]methane are also
exemplified.
Further, these compounds of which one configuration is
(4S) and other is (4R) among two bisoxazoline skeletons
such as 1-[2-[(4R)-methyloxazoline]-1-[2-[(4S)-
methyloxazoline]]methane are also exemplified.
These optically active bisoxazoline compounds (1) may
be used alone, or two or more kinds thereof may be used.
The optically active bisoxazoline compound (1) can be
produced by a method comprising contacting an optically
active diamide compound represented by the formula (8):

wherein R1, R2, R3, R4 and R5 are the same as described
above, which is obtained by reacting an optically active
aminoalcohol compound represented by the formula (6):

wherein R1, R2, and R3 are the same as described above, with
a compound represented by the formula (7):

wherein R4 and R5 are the same as described above and Z
represents an alkoxy group or a halogen atom, with a Lewis
acid, for example, as described in EP 895992 A.
In the formula of the boron compound represented by
the formula (2) (hereinafter, simply referred to as the
boron compound (2)) which is the component (C), A
represents a lithium atom, a sodium atom, a potassium atom,
a silver atom or a trityl group and the trityl group is
preferable. X represents a fluorine atom or a fluorine-
substituted C1-C8 alkyl group and n represents an integer
of 1 to 5. Examples of the fluorine-substituted C1-C8
alkyl group include a fluoromethyl, difluoromethyl,
trifluoromethyl, perfluoroethyl, perfluoropropyl,

perfluorobutyl, perfluoropentyl, perfluorohexyl,
perfluoroheptyl and perfluorooctyl group.
Examples of the boron compound (2) include lithium
tetrakis(4-fluorophenyl)borate, sodium tetrakis(4-
fluorophenyl)borate, potassium tetrakis(4-
fluorophenyl)borate, silver tetrakis(4-fluorophenyl)borate,
trityl tetrakis(4-fluorophenyl)borate, lithium
tetrakis(3,5-difluorophenyl)borate, sodium tetrakis(3,5-
difluorophenyl)borate, potassium tetrakis(3,5-
difluorophenyl)borate, silver tetrakis(3,5-
difluorophenyl)borate, trityl tetrakis(3,5-
difluorophenyl)borate, lithium tetrakis(3,4,5-
trifluorophenyl)borate, sodium tetrakis(3,4,5-
trifluorophenyl)borate, potassium tetrakis(3,4,5-
trifluorophenyl)borate, silver tetrakis(3,4,5-
trifluorophenyl)borate, trityl tetrakis(3,4,5-
trifluorophenyl)borate, lithium
tetrakis(pentafluorophenyl)borate, sodium
tetrakis(pentafluorophenyl)borate, potassium
tetrakis(pentafluorophenyl)borate, silver
tetrakis(pentafluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, lithium
tetrakis(pentafluorophenyl)borate, sodium
tetrakis(pentafluorophenyl)borate, potassium
tetrakis(pentafluorophenyl)borate, silver

tetrakis(pentafluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, lithium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, sodium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, potassium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, silver tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, trityl tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, lithium tetrakis[2,4,6-
tris(trifluoromethyl)phenyl]borate, sodium tetrakis[2,4,6-
tris(trifluoromethyl)phenyl]borate, potassium
tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, silver
tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, trityl
tetrakis[2,4,6-tris(trifluoromethyl)phenyl]borate, lithium
tetrakis[pentakis(trifluoromethyl)phenyl]borate, sodium
tetrakis[pentakis(trifluoromethyl)phenyl]borate, potassium
tetrakis[pentakis(trifluoromethyl)phenyl]borate, silver
tetrakis[pentakis(trifluoromethyl)phenyl]borate and trityl
tetrakis[pentakis(trifluoromethyl)phenyl]borate. In terms
of handling easily, trityl tetrakis(4-fluorophenyl)borate,
trityl tetrakis(3,5-difluorophenyl)borate, trityl
tetrakis(3,4,5-trifluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, trityl tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate, trityl tetrakis[2,4,6-
tris(trifluoromethyl)phenyl]borate and trityl
tetrakis[pentakis(trifluoromethyl)phenyl]borate are

preferable and
trityl tetrakis(pentafluorophenyl)borate and trityl
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate are more
preferable.
As the boron compound (2) , a commercial available
compound can be used as it is and the compound produced by
a known method described in JP 9-295984 A and the like may
be used. The boron compound (2) may be used alone, or two
or more kinds thereof may be used.
The amount of the component (B) to be used is usually
0.8 to 5 moles, preferable 0.9 to 2 moles relative to 1
mole of the component (A).
The amount of the component (C) to be used is usually
0.8 to 5 moles, preferable 0.9 to 2 moles relative to 1
mole of the component (A).
The asymmetric copper complex of the present invention
can be obtained by mixing the component (A), the component
(B) and the component (C). The mixing order is not
particularly limited and for example, it is carried out by
a method comprising mixing the component (A) and the
component (B) in a solvent followed by adding the component
(C) thereto and the like.
The operation of mixing is usually carried out in the
presence of a solvent. Examples of the solvent include a
halogenated hydrocarbon solvent such as dichloromethane,

1,2-dichloroethane, chloroform and carbon tetrachloride, an
aromatic hydrocarbon solvent such as toluene and xylene,
and an ester solvent such as ethyl acetate. When the
olefin represented by the formula (3) (hereinafter, simply
referred to as the olefin (3)) described below is a liquid,
the olefin (3) may be used as the solvent. The amount of
the solvent to be used is usually 10 to 500 parts by weight
relative to 1 part by weight of the copper compound.
The operation of mixing is usually carried out in an
atmosphere of an inert gas such as argon and nitrogen. The
temperature of mixing is usually -20 to 100°C.
The asymmetric copper complex can be isolated by
concentrating a solution obtained by mixing the component
(A), the component (B) and the component (C), and the
solution obtained may be used for the reaction of the
olefin (3) and the diazoacetic acid ester represented by
the formula (4) (hereinafter, simply referred to as the
diazoacetic acid ester (4)) described below without
isolating the asymmetric copper complex.
The optically active cyclopropanecarboxylate compound
represented by the formula (5) (hereinafter, simply
referred to as the optically active cyclopropane compound
(5)) is obtained by reacting the olefin (3) with the
diazoacetic acid ester (4) in the presence of the
asymmetric copper complex thus obtained.

In the formula of the olefin (3), R6, R7, R8 and R9 are
the same or different, and independently represent a
hydrogen atom; a halogen atom; a C1-C6 alkyl group which is
optionally substituted with a halogen atom or atoms, a C1-
C6 alkoxy group or groups, a C7-C12 aralkyloxy group or
groups, a C2-C10 acyloxy group or groups, a C2-C7
alkoxycarbonyloxy group or groups, or a C7-C11
aryloxycarbonyloxy group or groups; a C1-C6 alkenyl group
which is optionally substituted with a halogen atom or
atoms, or a C2-C7 alkoxycarbonyl group or groups; a C6-C10
aryl group which is optionally substituted with a C1-C6
alkoxy group or groups; a C7-C12 aralkyl group which is
optionally substituted with a C1-C6 alkoxy group or groups;
or a C2-C7 alkoxycarbonyl group which is optionally
substituted with a halogen atom or atoms, a C1-C6 alkoxy
group or groups, a C7-C12 aralkyloxy group or groups, a C2-
C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy
group or groups, or a C7-C11 aryloxycarbonyloxy group or
groups.
Examples of the halogen atom include a fluorine,
chlorine, bromine and iodine atom.
Examples of the halogen atom and the C1-C6 alkoxy
group of the C1-C6 alkyl group which is optionally
substituted with the halogen atom or atoms, the C1-C6
alkoxy group or groups, the C7-C12 aralkyloxy group or

groups, the C2-C10 acyloxy group or groups, the C2-C7
alkoxycarbonyloxy group or groups, or the C7-C11
aryloxycarbonyloxy group or groups are the same as those
exemplified above. Examples of the C7-C12 aralkyloxy group
include a benzyloxy, 4-methylbenzyloxy and (1-
naphthyl)methoxy group. Examples of the C2-C10 acyloxy
group include an acetoxy and benzoyloxy group. Examples of
the C2-C7 alkoxycarbonyloxy group include a
methoxycarbonyloxy, ethoxycarbonyloxy and tert-
butoxycarbonyloxy group. Examples of the C7-C11
aryloxycarbonyloxy group include a phenoxycarbonyloxy group.
Examples of the C1-C6 alkyl group which is optionally
substituted with the halogen atom or atoms, the C1-C6
alkoxy group or groups, the C7-C12 aralkyloxy group or
groups, the C2-C10 acyloxy group or groups, the C2-C7
alkoxycarbonyloxy group or groups, or the C7-C11
aryloxycarbonyloxy group or groups include a methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,
chloromethyl, fluoromethyl, trifluoromethyl, chloroethyl,
methoxymethyl, ethoxymethyl, n-propoxymethyl,
isopropoxymethyl, n-butoxymethyl, tert-butoxymethyl,
benzyloxymethyl, acetoxymethyl, benzoylmoxymethyl,
methoxycarbonyloxymethyl, ethoxucarbonyloxymethyl, tert-
butoxycarbonyloxymethyl and phenoxycarbonyloxymethyl group.
Examples of the C1-C6 alkenyl group which is

optioanlly substituted with the halogen atom or atoms or
the C2-C7 alkoxycarbonyl group or groups include an ethenyl,
1-propenyl, 2-propenyl, 2-methy1-propenyl, 1-butenyl, 2-
butenyl, 3-butenyl, 1-chloro-2-propenyl and 2-
methoxycarbony1-1-propenyl group.
Examples of the C6-C10 aryl group which is optionally
substituted with the C1-C6 alkoxy group or groups include a
phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 4-
methylphenyl, 3-(methoxymethyl)phenyl and 2,3-
dihydrobenzofuran-4-yl group.
Examples of the C7-C12 aralkyl group which is
optionally substituted with the C1-C6 alkoxy group or
groups include a benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-
methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-
methoxybenzyl, (1-naphthyl)methyl and (2-naphthyl)methyl
group.
Examples of the C2-C7 alkoxycarbonyl group which is
optionally substituted with the halogen atom or atoms, the
C1-C6 alkoxy group or groups, the C7-C12 aralkyloxy group
or groups, the C2-C10 acyloxy group or groups, the C2-C7
alkoxycarbonyloxy group or groups, or the C7-C11
aryloxycarbonyloxy group or groups include a
methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,
isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl and
n-pentyloxycarbonyl group.

When R6 and R8 represent the same in the formula of
the olefin (3), R6 and R7 represent different groups each
other.
Examples of the olefin (3) include propene,
fluoroethylene, 1-fluoro-1-chloroethylene, 1-butene,
isobutene, 1-pentene, 1-hexene, 1-octene, 4-chloro-1-butene,
2-pentene, 2-heptene, 2-methy1-2-butene, 2,5-dimethy1-2,4-
hexadiene, 2-chloro-5-methy1-2,4-hexadiene, 2-fluoro-5-
methy1-2,4-hexadiene, 1,1,1-trifluoro-5-methy1-2,4-
hexadiene, 2-methoxycarbony1-5-methy1-2,4-hexadiene, 1,1-
difluoro-4-methy1-l,3-pentadiene, 1,1-dichloro-4-methy1-
1,3-pentadiene, 1,1-dibromo-4-methy1-l,3-pentadiene, 1-
chloro-1-fluoro-4-methy1-1,3-pentadiene, 1-fluoro-1-bromo-
4-methy1-l,3-pentadiene, 2-methy1-2,4-hexadiene, 1-fluro-
1,1-dichloro-4-methy1-2-pentene, 1,1,1-trichloro-4-methy1-
3-pentene, 1,1,1-tribromo-4-methy1-3-pentene, 2,3-dimethy1-
2-pentene, 2-methy1-3-pheny1-2-butene, 2-bromo-2,5-
dimethy1-4-hexene, 2-chloro-2,5-dimethy1-4-hexene, 1-
chloro-2,5-dimethy1-2,4-hexadiene, (3-methy1-2-butenyl)
methyl ether, (3-methy1-2-butenyl) tert-butyl ether, (3-
methy1-2-butenyl) benzyl ether, 3-methy1-2-butenyl acetate,
3-methy1-2-butenyl benzoate, (3-methy1-2-butenyl) methyl
carbonate, (3-methy1-2-butenyl) tert-butyl carbonate, (3-
methy1-2-butenyl) phenyl carbonate, styrene and 4-viny1-
2,3-dihydrobenzofuran.

In the formula of the diazoacetic acid ester (4), R10
represents a C1-C6 alkyl group. Examples of the alkyl
group include a methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl and n-pentyl group. Examples of the diazoacetic
acid ester (4) include methyl diazoacetate, ethyl
diazoacetate, n-propyl diazoacetate, isopropyl diazoacetate,
n-butyl diazoacetate, isobutyl diazoacetate and tert-butyl
diazoacetate.
As the diazoacetic acid ester (4), those produced by a
known method such as Organic Synthesis Collective Volume 3,
p.392 can be used.
The amount of the asymmetric copper complex to be used
is usually 0.00001 to 0.5 mole, preferably in the range of
about 0.0001 to 0.05 mole in terms of the copper metal
relative to 1 mole of the diazoacetic acid ester (4).
The amount of the olefin (3) to be used is usually 1
mole or more, preferably 1.2 moles or more relative to 1
mole of the diazoacetic acid ester (4). There is no
specific upper limit and, when the olefin (3) is a liquid,
excess amount thereof, for example, about 100 moles
relative 1 mole of the diazoacetic acid ester (4), may be
used as the solvent.
The reaction of the olefin (3) and the diazoacetic
acid ester (4) is usually carried out in an atmosphere of
an inert gas such as argon and nitrogen. Since water

adversely affects the reaction, the reaction is preferably
carried out with suppressing the amount of water present in
the reaction system. As a method for suppressing the
amount of water present in the reaction system, method
comprising making a dehydrating agent such as molecular
sieves, magnesium sulfate and sodium sulfate anhydride
coexist in the reaction system, and using the olefin (3) or
the solvent previously subjected to dehydration treatment.
The reaction temperature is usually about -50 to 150°C,
preferably about -20 to 80°C.
The reaction of the olefin (3) and the diazoacetic
acid ester (4) is usually carried out by mixing the
asymmetric copper complex, the olefin (3) and the
diazoacetic acid ester (4), and if necessary, in the
presence of a solvent. The mixing order is not
particularly limited. Usually, the asymmetric copper
complex and the olefin (3) are mixed in the solvent and
then the diazoacetic acid ester (4) is added thereto.
Examples of the solvent include a halogenated
hydrocarbon solvent such as dichloromethane, 1,2-
dichloroethane, chloroform and carbon tetrachloride, an
aliphatic hydrocarbon solvent such as hexane, heptane and
cyclohexane, an aromatic hydrocarbon solvent such as
toluene and xylene, and an ester solvent such as ethyl
acetate. They can be used alone or in the form of a mixed

solvent. As described above, when the olefin (3) is a
liquid, the olefin (3) may also be used as the solvent.
When the solvent is used, the amount of the solvent to be
used is not particularly limited, and in viewpoint of the
volume efficiency and the properties of the reaction
mixture, the amount thereof is usually about 2 to 30 parts
by weight, preferably about 4 to 20 parts by weight
relative to 1 part by weight of the diazoacetic acid ester
(4).
When the asymmetric copper complex prepared using the
divalent copper compound as the component (A) is used, a
reducing agent such as phenylhydrazine may be used together.
After completion of the reaction, the optically active
cyclopropane compound (5) can be isolated by, for example,
distilling the reaction mixture. The optically active
cyclopropane compound (5) isolated may be further purified,
if necessary, by a conventional purification means such as
column chromatography.
Examples of the optically active cyclopropane compound
(5) include optically active methyl 2-
fluorocyclopropanecarboxylate, optically active methyl 2-
fluoro-2-chlorocyclopropanecarboxylate, optically active
methyl 2-methylcyclopropanecarboxylate, optically active
methyl 2,2-dimethylcyclopropanecarboxylate, optically
active methyl 2,2-dimethy1-3-(2-methy1-1-

propenyl)cyclopropanecarboxylate, optically active methyl
2,2-dimethy1-3-(2,2-dichloroethenyl)cyclopropanecarboxylate,
optically active methyl 2,2-dimethy1-3-(2,2,2-
trichloroethyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2,2,2-
tribromoethyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2,2-
dibromoethenyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2, 2-
difluoroethenyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2-fluoro-2-
chloroethenyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2-fluoro-2-
bromoethenyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2-fluoro-1-
propenyl)cyclopropanecarboxylate, optically active methyl
2,2-dimethy1-3-(2-chloro-1-propenyl)cyclopropanecarboxylate,
optically active methyl 2,2-dimethy1-3-(2-chloro-2-
trifluoromethylethenyl)cyclopropanecarboxylate, optically
active methyl 2,2-dimethy1-3-(2-methoxycarbony1-1-
propenyl)cyclopropanecarboxylate, optically active methyl
2,2-dimethy1-3-(2-chloro-2-
methylpropyl)cyclopropanecarboxylate, optically active
methyl 2,2-dimethy1-3-(2-bromo-2-
methylpropyl)cyclopropanecarboxylate, optically active

methyl 2,2-dimethy1-3-(1-propenyl)cyclopropanecarboxylate,
optically active methyl 3,3-dimethy1-2-
(methoxymethyl)cyclopropanecarboxylate, optically active
methyl 3,3-dimethy1-2-(tert-
butoxymethyl)cyclopropanecarboxylate, optically active
methyl 3,3-dimethy1-2-
(benzyloxymethyl)cyclopropanecarboxylate, optically active
methyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate, optically active
methyl 3,3-dimethy1-2-
(benzoyloxymethyl)cyclopropanecarboxylate, optically active
methyl 3,3-dimethy1-2-
(methoxycarbonyloxymethyl)cyclopropanecarboxylate,
optically active methyl 3,3-dimethy1-2-(tert-
butoxycarbonyloxymethyl)cyclopropanecarboxylate, optically
active methyl 3,3-dimethy1-2-
(phenoxycarbonyloxymethyl)cyclopropanecarboxylate,
optically active methyl 2-phenylcyclopropanecarboxylate and
optically active methyl 2-(2,S-dihydrobenzofuran^-
ylJcyclopropanecarboxylate; and compounds wherein the above
methyl ester moieties are replaced with ethyl, n-propyl,
isopropyl, isobutyl or tert-butyl ester moieties.
Examples
In the following Examples, the yield was calculated

based on the diazoacetic acid ester by the gas
chromatography internal standard method. The trans-
isomer/cis-isomer ratio was calculated based on the area
ratio of the gas chromatography. The optically purity was
calculated based on the area ratio of the liquid
chromatography. The trans-isomer means the compound having
the ester group at 1-position and the substituent at 2-
position on the opposite side with respect to the
cyclopropane ring plane and the cis-isomer means the
compound having the ester group at 1-position and the
substituent at 2-position on the same side.
Example 1
Into a 50 ml Schlenk tube purged with nitrogen, 1.98
mg of copper(I) chloride, 6.43 mg of 1,1-bis[2-[(4S)-(tert-
butyl)oxazoline]]cyclopropane and 5 ml of 1,2-
dichloroethane were charged. To the pale yellow mixture
obtained by mixing them, 20.29 mg of trityl
tetrakis(penntafluorophenyl)borate was added and the
resulting mixture was stirred at room temperature for 10
minutes to obtain the yellow homogeneous solution
containing the asymmetric copper complex. The ultraviolet
absorption spectrum of the solution was measured to confirm
the generation of new peaks at 290 nm, 350 nm, and 740 nm.
The solution was analyzed by gas chromatography to confirm

the production of trityl chloride.
After 10.25 g of 3-methy1-2-butenyl acetate was added
to the homogeneous solution containing the asymmetric
copper complex obtained and the inner temperature was
adjusted to 20°C, 5 ml of the 1,2-dichloroethane solution
containing ethyl diazoacetate (concentration: 4 mol/1) was
added dropwise thereto over 4 hours and the resulting
mixture was reacted at the same temperature for 30 minutes
to obtain the solution containing ethyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate.
Yield: 80%
Trans-isomer/cis-isomer ratio: 89/11
Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis-
isomer 5%e.e. ((-)-isomer)
Example 2
According to the same manner as that described in
Example 1, the solution containing ethyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate was obtained except
that 24.32 mg of trityl tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate was used in place of
20.29 mg of trityl tetrakis(pentafluorophenyl)borate.
Yield: 81%
Trans-isomer/cis-isomer ratio: 88/12
Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis-

isomer 9%e.e. ((+)-isomer)
Example 3
According to the same manner as that described in
Example 1, the solution containing ethyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate was obtained except
that 2.69 mg of copper(II) chloride was used in place of
1.98 mg of copper(I) chloride.
Yield: 78%
Trans-isomer/cis-isomer ratio: 89/11
Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis-
isomer 4%e.e. ((-)-isomer)
Comparative Example 1
Into a 50 ml Schlenk tube purged with nitrogen, 5.17
mg of copper(I) trifluoromethanesulfonate toluene complex,
6.43 mg of 1,1-bis[2-[(4S)-(tert-
butyl)oxazoline]]cyclopropane and 5 ml of 1,2-
dichloroethane were charged and the resulting mixture was
stirred at room temperature for 10 minutes to obtain the
yellow homogeneous solution containing the asymmetric
copper complex. After 10.25 g of 3-methy1-2-butenyl
acetate was added thereto and the inner temperature was
adjusted to 20°C, 5 ml of the 1,2-dichloroethane solution
containing ethyl diazoacetate (concentration: 4 mol/1) was

added dropwise thereto over 4 hours and the resulting
mixture was reacted at the same temperature for 30 minutes
to obtain the solution containing ethyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate.
Yield: 60%
Trans-isomer/cis-isomer ratio: 81/19
Optically purity: trans-isomer 92%e.e. ((+)-isomer), cis-
isomer 65%e.e. ((+)-isomer)
Example 4
According to the same manner as that described in
Example 1, the solution containing ethyl 3,3-dimethy1-2-
(benzyloxymethyl)cyclopropanecarboxylate was obtained
except that 7.08 g of (3-methy1-2-butenyl) benzyl ether was
used in place of 10.25 g of 3-methy1-2-butenyl acetate.
Yield: 89%
Trans-isomer/cis-isomer ratio: 92/8
Optically purity: trans-isomer 95%e.e. ((+)-isomer), cis-
isomer 3%e.e. ((-)-isomer)
Comparative Example 2
According to the same manner as that described in
Comparative Example 1, the solution containing ethyl 3,3-
dimethy1-2-(benzyloxymethyl)cyclopropanecarboxylate was
obtained except that 7.08 g of (3-methy1-2-butenyl) benzyl

ether was used in place of 10.25 g of 3-methy1-2-butenyl
acetate.
Yield: 71%
Trans-isomer/cis-isomer ratio: 84/16
Optically purity: trans-isomer 88%e.e. ((+)-isomer), cis-
isomer 52%e.e. ((-)-isomer)
Example 5
According to the same manner as that described in
Example 1, the solution containing ethyl 3,3-dimethy1-2-
(acetoxymethyl)cyclopropanecarboxylate was obtained except
that the amount of 3-methy1-2-butenyl acetate to be used
was 20.50 g and the amount of the 1,2-dichloroethane
solution containing ethyl diazoacetate (concentration: 4
mol/1) to be used was 10 ml.
Yield: 74%
Trans-isomer/cis-isomer ratio: 86/14
Optically purity: trans-isomer 93%e.e. ((+)-isomer), cis-
isomer 12%e.e. ((-)-isomer)
Comparative Example 3
According to the same manner as that described in
Comparative Example 1, the solution containing ethyl 3,3-
dimethy1-2-(acetoxymethyl)cyclopropanecarboxylate was
obtained except that the amount of 3-methy1-2-butenyl

acetate to be used was 20.50 g and the amount of the 1,2-
dichloroethane solution containing ethyl diazoacetate
(concentration: 4 mol/1) to be used was 10 ml.
Yield: 43%
Trans-isomer/cis-isomer ratio: 80/20
Optically purity: trans-isomer 93%e.e. ((+)-isomer), cis-
isomer 61%e.e. ((-)-isomer)
Industrial Applicability
According to the process of the present invention, an
optically active cyclopropanecarboxylate compound, which is
useful as a synthetic intermediate of pesticides and
pharmaceuticals such as synthesized pyrethroid insecticides,
can be obtained.

1. An asymmetric copper complex obtained by mixing
(A) at least one monovalent or divalent copper
compound,
(B) at least one optically active bisoxazoline
compound represented by the formula (1):

wherein R1 and R2 are the same or different, and
independently represent a hydrogen atom; a C1-C6 alkyl
group; a phenyl group which is optionally substituted with
a C1-C6 alkyl group or groups, or a C1-C6 alkoxy group or
groups; or a C7-C12 aralkyl group which is optionally
substituted with a C1-C6 alkoxy group or groups, or R1 and
R2 are bonded together to represent a C2-C6 polymethylene
group,
R3 represents a methyl group; an isopropyl group; an
isobutyl group; a tert-butyl group; a 1-naphthyl group; a
2-naphthyl group; a phenyl group which is optionally
substituted with a C1-C6 alkyl group or groups, or a C1-C6
alkoxy group or groups; or a C7-C12 aralkyl group which is

optionally substituted with a C1-C6 alkoxy group or groups,
and
R4 and R5 are the same and represent hydrogen atoms or C1-
C3 alkyl groups, or R4 and R5 are bonded together to
represent a C2-C5 polymethylene group, and
(C) at least one boron compound represented by the
formula (2):

wherein A represents a lithium atom, a sodium atom, a
potassium atom, a silver atom or a trityl group, X
represents a fluorine atom or a fluorine-substituted C1-C8
alkyl group, and n represents an integer of 1 to 5.
2. The asymmetric copper complex according to claim
1, wherein the component (A) is at least one monovalent
copper compound.
3. The asymmetric copper complex according to claim
1, wherein the copper compound is a copper halide in the
component (A).
4. The asymmetric copper complex according to claim

1, wherein A is the trityl group in the component (C).
5. A process for production of an optically active
cyclopropanecarboxylate compound represented by the formula

wherein R6, R7, R8 and R9 are the same or different, and
independently represent a hydrogen atom; a halogen atom; a
C1-C6 alkyl group which is optionally substituted with a
halogen atom or atoms, a C1-C6 alkoxy group or groups, a
C7-C12 aralkyloxy group or groups, a C2-C10 acyloxy group
or groups, a C2-C7 alkoxycarbonyloxy group or groups, or a
C6-C10 aryloxycarbonyloxy group or groups; a C1-C6 alkenyl
group which is optionally substituted with a halogen atom
or atoms or a C2-C7 alkoxycarbonyl group or groups; a C6-
C10 aryl group which is optionally substituted with a C1-C6
alkoxy group or groups; a C7-C12 aralkyl group which is
optionally substituted with a C1-C6 alkoxy group or groups;
or a C2-C7 alkoxycarbonyl group which is optionally
substituted with a halogen atom or atoms, a C1-C6 alkoxy
group or groups, a C7-C12 aralkyloxy group or groups, a C2-
C10 acyloxy group or groups, a C2-C7 alkoxycarbonyloxy
group or groups, or a C6-C10 aryloxycarbonyloxy group or
groups; provided that, when R6 and R8 represent the same, R6
and R7 represent different groups each other; and R10
represents a C1-C6 alkyl group.

which comprises reacting an olefin represented by the
formula (3):

wherein R6, R7, R8 and R9 are as described above,
with a diazoacetic acid ester represented by the formula
(4):

wherein R10 is as described above,
in the presence of the asymmetric copper complex described
in claim 1.
6. The process according to claim 5, wherein in the
formula (3),
(a) R6 and R8 are methyl groups, R7 is a hydrogen atom; a
C1-C6 alkyl group substituted with a C7-C12 aralkyloxy
group or groups, or a C2-C10 acyloxy group or groups; or a
C1-C6 alkenyl group which is optionally substituted with a
halogen atom or atoms, and R9 is a hydrogen atom or
(b) R6 and R8 are hydrogen atoms, R7 is an aryl group which
is optionally substituted with a C1-C6 alkoxy group or
groups; or a halogen atom, and R9 is a hydrogen or halogen
atom.
7. The process according to claim 5, wherein in the
formula (3),

(a) R6 and R8 are methyl groups, R7 is a hydrogen atom, a
benzyloxymethyl group, an acetoxymethyl group, a 2-methy1-
1-propenyl group, a 2,2-dichloroethenyl group, a 2.2-
dibromoethenyl group or 2-chloro-2-fluoroethenyl group, and
R9 is a hydrogen atom or
(b) R6 and R8 are hydrogen atoms, R7 is a 2,3-
dihydrobenzofuran-4-yl group or a fluorine atom, and R9 is
a hydrogen or fluorine atom.

A process for production of an optically active
cyclopropanecarboxylate compound represented by the formula
(5):

wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or
the like and R10 represents a C1-C6 alkyl group,
which comprises reacting an olefin represented by the
formula (3):

wherein R6, R7, R8 and R9 are as described above,
with a diazoacetic acid ester represented by the formula
(4):

wherein R10 is as described above,
in the presence of an asymmetric copper complex obtained by
mixing
(A) at least one monovalent or divalent copper
compound.

(B) at least one optically active bisoxazoline
compound represented by the formula (1):

wherein R1 and R2 represent a C1-C6 alkyl group or the
like; R3 represents a tert-butyl group or the like; and R4
and R5 are the same and represent C1-C3 alkyl groups or the
like, and
(C) at least one boron compound represented by the
formula (2):

wherein A represents a trityl group or the like, X
represents a fluorine atom or the like, and n represents an
integer of 1 to 5.

AN ASYMMETRIC COPPER COMPLEX AND A PROCESS FOR MAKING THE SAME

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