Title of Invention	A CHIRAL COPPER COMPLEX CATALYST COMPOSITION
Abstract	There is disclosed chiral copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of fornlula (1): with a mono-valent or di-valent copper compound in an inert solvent, wherein R<SUB>l and R<SUB>2 represent an alkyl group and the like, X<SUB>l and X<SUB>2 represent a hydlrogen atom, a halogen atom. a nitro group, an alkyl group, an alkoxy group. a cyano group or the like, and the amount of the mono-valent or di-valent c.opper compound is less than 1 nlole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and a process for producing an optically active cylopropane-carboxylic acid ester using the same.

Title of Invention

A CHIRAL COPPER COMPLEX CATALYST COMPOSITION

Abstract

There is disclosed chiral copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of fornlula (1): with a mono-valent or di-valent copper compound in an inert solvent, wherein R<SUB>l and R<SUB>2 represent an alkyl group and the like, X<SUB>l and X<SUB>2 represent a hydlrogen atom, a halogen atom. a nitro group, an alkyl group, an alkoxy group. a cyano group or the like, and the amount of the mono-valent or di-valent c.opper compound is less than 1 nlole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and a process for producing an optically active cylopropane-carboxylic acid ester using the same.

Full Text	The prsent invention R6lates to a production process for asymmetR1c synthesis of cyclopropane-carboxylic acid compound using a chiR3l copper complex catalyst. As a process for producing an optically active cyclopropanecarboxylic acid ester deR1vative, theR6 has been R6ported a process of using a chiR3l copper complex catalyst which was pR6paR6d by R6acting equivalent or excess amount of cupR1c salt with optically active salicylideneaminoalcohol (JP-B 53-43955, JP-A 50-151842, JP- A 54-73758 and JP-A 59-225194). However, in the disclosed processes said copper complex R6quiR6d puR1fication by R6crystallization or washing with methanol or the like to R6move an excessive amount of copper compound. According to the pR6sent invention, a chiR3l copper complex catalyst composition can be obtained in an industR1ally advantageously and can be used in an asymmmetR1c cyclopropanation R6action with good R6producibility. Our co-pending application 63/MAS/2001 R6lates to "An optically active saUcylideneaminoalcohol compound". The pR6sent invention provides a chiR3l copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of formula (1): with a mono-valent or di-valent copper compound in an inert solvent, wheR6in R1 R6pR6sents an alkyl group which may be substituted with a group selected from an alkoxy group, an aR3lkyloxy group, an aryloxy group, and cycloalkoxy group, an aR3lkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aR3lkyloxy group, an aryloxy group, and a cycloalkoxy group, R2 R6pR6sent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aR3lkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aR3lkyloxy group, an aryloxy group, and a cycloalkoxy group, X1 and X2 aR6 the same or diffeR6nt and independently R6pR6sent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group, and two adjacent X1 and X2 together with the benzene R1ng to which they aR6 bonded may form a l-hydroxy-2- or 2,-hydroxy-l-naphthyl group, and the carbon atom denoted by " * " is an asymmetR1c carbon atom having either an S or R configuR3tion, and the amount of the mono-valent or di-valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and a process for producing an optically active . cyclopropanecarboxylic acid ester of formula (2)" wheR6in R3, R4, R5 and R6 aR6 as defined below, and R7 R6pR6sents an alkyl group having I to 8 carbon atoms, a cycloalkyl group which may be optionally substituted with a lower alkyl group, a benzyl group or phenyl group which may be optionally substituted with a lower alkj"l group, a lower alkoxy group or a phenoxy group, which compR1ses the steps of (a) contacting an optically active N-salicylideneaminoalcohol compound of formula (!): with a mono"valent or di-valenl copper compound in an inert solvent, wheR6in R1, R2, X1, X2 and " * " have the same meanings as defined above, and the amount of the monovalent or di-valent copper compound is h?ss than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (l), and (b) R6acting a prochiR3l olefin of formula (3)" wheR6in R3, R4. R5 and R6 independently R6pR6sent a hydrogen atom, a halogen atom, a (Cl-C10)alkyl group which may be substituted with a halogen atom or a lower alkoxy group, a (C4-C8)cycloalkyl group, an aryl group which may be substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group, R3 and R4, or R5 and R6 may be bonded at their terminals to form an alkylene group having 2-4 carbon atoms, and one of R2, R4, R5 and R6 groups R6pR6sents an alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy carbonyl group, of which alkoxy may be substituted with a halogen atom or atoms provided that when R3 and R6 aR6 the same, R4 and R6 aR6 not the same, with a diazoacetic acid ester of formula (4): N2CHCO2R7 (4) wheR6in R7 is the same as defined above, in the pR6sence of a chiR3l copper complex catalyst composition so produced in step (a). Detailed DescR1ption FiR3t, a descR1ption will be made to the optically active salicylideneaminoalcohol compound of formula (l) as defined above. Examples of the alkyl group which may be substituted with a group selected from an alkoxy group, an aR3lkyloxy group, an aryloxy group and a c3"cloalkoxy group, R6pR6sented by R1, include a (Cl-C8)alkyl group (e.g., a methyl, ethyl, n-propyl, i-propyl, n-butyl. rbutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-pentyl, n-octyl, n-nonyl, or n-decyl group) which may be substituted with a group selected from a (Cl-C4)alkoxy group(e.g., a methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, secbutoxy or t"butoxy group), a (C7-Cll)aR3lkyIoxy group(e.g., a benzyloxy or naphthylmethyloxy group), a (C6-Cll)aryloxy groupCe.g., a phenoxy or naphthoxy group), a (C4-C6)cycloalkoxy groupCe.g., a cyclobutyloxy, cyclopentyloxy or cyclohexyloxy group) and the like. Examples of the aR3lkyl group, the aryl group and the cycloalkyl group, all of which may be sub.stituted with a group selected from an alkyl group, an alkoxy group, an aR3lkyloxy group, an aryloxy group and a cycloalkoxy group include a (C7-Cll)aR3lkyl groupCe.g., a benzyl, or naphthylmethyl group), a (C6-C10)aryl groupCe.g., a phenyl, or naphthyl group), a (C4"C6)cycloalkyl groupCe.g., a cyclobutyl, cyclopentyl, or cyciohexyl group), all of which may be substituted with the CCl-C8)alkyl, CC7-Cll)aR3lkyloxy, CCB-ClDaryloxy and (C4-C6)cycloalkoxy group as specified above and a CClC8)alkoxy groupCe.g, , a methoxy, ethoxy, n-propoxy, i-propoxy, nbutoxy, ibutoxy, sec-butoxy, t-butoxy, n-pentoxy, nhexyloxy, npentyloxy or n-octyloxy group). The alkyl group R6pR6sented by R2 include said (Cl-C8)alkyl group as above. The cycloalkyl group R6pR6sented by R2 include said (C4-C6)cycloalkyl group ae above. The aR3lkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aR3lkj"loxy group, an aryloxy group and a cydoalkoxy group R6pR6sented by R2 include the same meanings as defined above for the groups R6pR6sented by R1 The subetituent group X1 and X2 of the salicylideneaminoalcohol compound of formvila (l) will be explained below. Exampleis of the halogen atom R6pR6sented by X1 and X2 include a fluoR1ne atom, a chloR1ne atom and a bromine atom. Examples of the alkj"l group include a (Cl-CS) alkyl group such as a methyl, ethyl, npropyl, i"propyl, n"butyl, tbntyl, sec-butyl, n-pentyl, nhexyl, n-heptyl, n-octyl and the like. Examples of the alkoxy group include the same (Cl-C4)alkoxy group as defined above in the alkoxy group for R1 In salicylideneaminoalcohol compound of formula (1), pR6ferR6d aR6 a salicylideneaminoalcohol compound (1) in which X1 R6pR6sents a bromine atom and X2 is a hydrogen atom or a bromine atom, a salicyhdeneaminoalcohol compound (1) in which X1 R6pR6sents a nitro group and X2 is a hydrogen atom, a methjd group or a methoxy group, a salicylideneaminoalcohol compound (l) in which X1 R6pR6sents a chloR1ne atom and X2 is a chloR1ne atom, and a salicylideneaminoalcohol compound (l) in which X1 is a hydrogen atom and X2 is a fluoR1ne atom. MoR6 pR6ferR6d aR6 a salicylideneaminoalcohol compound (l) in which X1 R6pR6sents a nitro group or a bromine atom and X2 is a hydrogen atom, a salicylidenGammoalcohol compound (1) in which X1 R6pR6sents a chloR1ne atom and X2 is a chloR1ne atom, and a salicylideneaminoalcohol compound (1) in which X1 is a hydrogen atom and X2 is a fluoR1ne atom. Among the optically active salicylideneaminoalcohol compound of formula (1), R1 is pR6feR3bly an alkyl group having 1 to 6 carbon atoms, an aR3lkyl, an aryl group, and R3 is pR6feR3bly an alkyl group (e.g. lower alkyl groups having 1 to 6 carbon atoms), an aR3lkyl group (e.g., a benzyl group), an aryl group (e.g., a phenyl group, a 2-methoxyphenyl group, a 2 tert-butoxy-5-tert-butylphenyl group or a 2"OCtyloxy"5-t6rt-butylphenyl group). Specific examples the optically active salicylideneaminoalcohol compound of formula (l) include optically active N-salicyliden"2-ainino-l,l"diphenyM-propanol, i^-aalicyliden-2-amino-l,l-di(2-methoxyphenyl)-l-propanol, N-salicyliden-2aminO"l,l"di(2"isopropoxyphenyl)"l-propanol, N-6alicyUden-2"amino-1, l-di(2butoxy-S-t-butj"lphenyl)- l-propanol, N-salicyliden-2"amino"l,l-diphenyl"3-phenyM"propanol, N-salicyliden-2amino" 1, l-di(2"methoxyphenyl)"3-phenyl- 1-propanol, N-salicyliden-2-amino-l,l-di(2isopropoxyphenyl)-3-phenyM"propanol, N"salicyliden-2"amino-l,l"di(2-butoxy-6-t-butylpbenyl)-3"phGnyl"l-propanol, N"8alicyliden-2-amino-l,l-di(2 methoxyphenyl)"3-phenyM-butanol, N"(3 fluorosalicyliden)-2-aminol,l"di(2-butoxy-5-tbutylphenyl)-l"propanol, N"(3 fluoro8alicyliden)-2-aR3ino-l,l-di(2-octyloxy-5-t-butylphenyl)"l-propanol, N(3-fluorosalicj"liden)-2"amino-l,l"di(2-butoxy5-t-butylphenyD-3"phenyM-propanol, N-(3-fluorosalicyUden)-2-aminol,ldi(2-m6thoxj"plienyl)-l-propanol, N-(3-fluoro8alicyUden)-2-amino" 1,1 ■diphenyM"propanol, N-(3"fluorosalicyliden)-2-aminO"l,ldi(2"benzyloxy-5-methylphenyl)"3-(4-iso-propoxyphenyi)-Ipropanol, N-(3-fluoro8alicyliden)-2-aminol,l"diphenyl-3"phenyM-propanol, N-(3fluorosalicyliden)-2-amino"l,l"di(2"methoxyphenyl)"3"methyM"butanol, N-(3-fluorosaliq"liden)-2-amino-3-phenyMpropanol, N (3,5-dichlorosalicylidene)-2amino-l,l"diphenylpropanol, N"(3.5-dichlorosalicylidene)-2-aminol,l-di-(2-R3ethoxyphenyDpropanol N"-(3.5-dichlorosalicylidene)-2-amino-l,l-di(5"tert-butyl-2-tert-butoxyphenyl)- 3-phenyl- Ipropanol, N-(3,5-dichlorosalicylidene)-2-amiiiO"l,l-di"(5-terfbutyl-2 octyloxyphenyl)- propanol N-(5-bromosalicyliden)-2-amino-l.l"diphenyl-l-propanol, N"(5-bromosalicyliden)-2-ammo-l,l-di(2-methoxypheiiyl)"l-propanoI, N-(3,5-dibroinosalicyUden)-2-ainino"l,l-diphenyl-l-pi"opanol, N(5-nitrosalicyliden)"2"amino-l,l-diph6nyM-propanol, N-(5-nitrosalicyliden)-2-ammo-l,l"diphenyl-3-phenyM-propanol, N"(5-nitroBalicyliden)"2-ainino-l.l-di(2-butoxy5"t-butylplienyl)-3-phenyl- propanol, N-(5-nitrosalicyliden)-2"aminoX,l"di(2-benzyloxy5-methylphenyl)-3-(4-i80- propoxjTphenyl) ■ 1 -propanol, N-(5nitroaalicyliden)-2-aminol,l-di(2-methoxyphenyl)"l-propanol, N-(5-nitrosalicyliden)"2-amino-1, l-di(2-t-b utyl-4-methylphenyl)-3-phenyM propanol, N-(5-nitrosalicyliden)-2-amino-l,l-di(2-butoxy5-t-butylphenyl)-l-propanol, N"(5-nitrosalicyliden)-2-amino"l,l-di(2methoxyphenyl)-3-xnethyMbutanol, N-(5"nitro8alicylidene)"2-amino"l,l-dr(5-tert"butyl-2"octyoxyphenyl)l" propanol, N (5-nitro8alicylidene)"2-ajaino-l,l-di(5-tert-butyl-2-tert-butoxyph6nyl)-3- phenyl" 1-propanol, N-(3-methoxy-5-mtrosalicyliden)-2-ainino-l,l-di(2"butoxy-5-t"butylph6nyl )-1- propanol, N-(3-methoxy5-nitrosaIicylideu)-2"aR3ino"l,l-di(2"methoxyphenyl)"l- propanol, N-(3-methoxy 5-mtrosalicyliden)"2-amino- 1,1-diphenyl ■ 1-propanol, N-(3"t-butylsalicyliden)2-aniino-l,l"diphenyM-propanoI, N"(3,5-drtbutylsalicyliden)2-amino-l,l-di(2-methoxyphenyl)-l-propanol, and the like. Said optically active compounda may have either an S configuR3tion or R configuR3tion with R6spect to the carbon atom denoted by" " in the formula above. The salicylidenaminoalcohol of formula (l) is usually contacted with a mono"valent or di-valent copper compound to produce a chiR3l copper complex in an inert solvent. Examples of the mono-valent or di-valent copper compound include a copper salt of an organic carboxylic acid having 2 to 15 carbon atoms such as copper acetate, copper naphthenate, copper octanoate and the like, and a copper salt such as copper chloR1de, copper bromide, copper nitR3te, copper sulfate, copper methanesulfonte, copper tR1fluoromethanesulfonate, copper cyanate, copper carbonate and copper oX1de, and a mixtuR6 theR6of. Examples of the inert solvent include a hydrocarbon such as hexane, heptane, cyclohexane or the like, an ester such as methyl acetate, ethyl acetate, ethyl propionate or the like, a ketone such as acetone, methyl ethyl ketone or the like, a halogenated hydiocarbon such as butyl chloR1de, dichloroethane, chloroform, carbon tetR3chloR1de or the like, and an aromatic hydrocarbon such as toluene, xylene or the like. The mixtuR6 of solvent descR1bed above can be also used. An amount theR6of to be used is not particularly limited. ProchiR3l olefins of formula (3) to be used in the next cyclopropanation step may also be used as a solvent. An amount of the copper compound to be used is less than 1 mole, usually 0.2 to 0.95 mole, pR6feR3bly 0.4 to 0.94 mole per mol of the optically active salicylideneaminoalcohol compound of fonnula (1). The R6action tetopeR3tuR6 is usually room tempeR3tuR6 to the boiling point of the solvent used, or typically 10 to 100°C. The R6action mixtuR6, which is the pR6sent chiR3l copper complex catalyst composition, can be used as it is for the asymmetR1c synthesis, or it may be concentR3ted to a suitable concentR3tion, if necessary. The chiR3l copper catalyst composition thus obtained usually contains 0,1 to 30 (wt)% of the chiR3l copper complex which is deR1ved from the slicylideneamiuoalcohol compound of formula (1) and the copper compound, and the inert solvent. It can also be used after the isolation by R6moving the solvent. Alternatively, the R6sulting R6action mixtuR6 may be further contacted with a base, if necessary. Examples of the base include an alkali metal alcoholate such as sodium methylate and sodium ethylate, which can be used as they are as powdeR3 or as a solution in alcohol such as methanol, ethanol or the like, alkali metal hydroX1de such as sodium hydroX1de, potassium hydroX1de or the like, alkali metal carbonate or bicarbonate such as sodium carbonate, sodium bicarbonate and the like. These aR6 usually used as an aqueous solution. The amount of the base to be used is usually 0.1-8 moles, pR6feR3bly around 0.5-3 moles per mole of the copper compound. Although the R6sulting R6action mixtuR6 can be used as it is without R6movmg a salt produced by neutR3lization of them (for example, sodium acetate in the case of using copper acetate, sodiiun naphthenate in the case of using copper naphthenate), it is pR6feR3bly used after R6moving the salt by washing with water. In this case, the catalyst may be used after being dehydR3ted. Thus obtained chiR3l copper complex catalyst composition in a solution form, of which concentR3tion is usually within the R3nge of the concentR3tion as descR1bed above, optionally adjusted by concentR3tion or addition of an appropR1ate solvent, can be used in the cyclopropanation R6action, hence a puR1fying step is not particularly necessary. Although the product can be isolated by R6moving the solvent, the solution is usually used as it is and, theR6foR6, the pR6sent catalyst composition is suitably used in a continuous R6action process because of R6ady feeding of catalyst. Although the structuR6 of an asymmetR1c copper complex catalyst obtained heR6in is not always clearly established, it shows pR3ctically good activity for an industR1al production process. Next, a descR1ption will be made to the step of producing optically active cyclopropane-carboxylic acid ester of formula (2) as defined above, which step compR1sing R6acting a prochiR3l olefin of formula (3) with a diazoacetic acid ester of formula (4) in the pR6sence of a chiR3l copper complex catalyst composition so produced. R3, R4, R3 or R6 of the prochiR3l olefin of formula (3) will be explained below. Examples of the alkyl group which may be substituted with a halogen atom or an alkoxy group include a linear or bR3nched alkyl group having 1 to 10 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n"decyl group, an alkyl group substituted with a halogen atom such as a fluoR1ne atom, a chloR1ne atom, a bromine atom and the like a haloalkyl group such as a chloromethyl, dichloromethyl, tR1chloromethyl, difluoromethyl, tR1fluoromethyl, 2,2,2-tR1chloroethyl group or the like, an alkyl group substituted with an alkoxy group such as a methoxy, ethoxy, n-propoxy, ipropoxy group or the like. Examples of the alkylene group formed by R3 and R4, or R5 and R6 include ah alkylene group having 2 to 4 carbon atoms such as dimethylnene, tR1methylene, or tetR3methylene group. Examples of the alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy cax"bonyl group, of which alkoxy may be substituted with a halogen atom or atoms, R6pR6sented by R3, R4, R3 include a linear or bR3nched alkenyl groups having 1 to 10 carbon atoms such as an ethenyl, propenyl, 2-methylpropenyl, 1-butenyl, 2-butenyl, or hexenyl group, a haloalkenyl group, which is the above"descR1bed alkenyl group substituted with the above-descR1bed halogen atom or atoms, such as a chloroethenyl group, a chloropropenyl group, 2,2-dicshlor6ethenyl group, 2,2-difluoroethenyl group or the like, an alkoxy(Cl-C3)carbonyl substituted alkenyl group such as 2-methoxycarbonyl"2-methylethenyl group, 2(1,1,1,3,3,3"hexafluoroisopropoxycarbonyl)-1-methylethenyl group or the like. Specific examples of the prochiR3l olefin (3) include propene, l"butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 4-chloro-l-butene, 2"pentene, 2-heptene, 2"methyl"2-butene, 2,5"dimethyl"2,4-hexadiene, 2"chloro-5-methyl-2,4"hexadiene, 2-fluoro-5"methyl2,4"hGxadiene, l,l,l-tR1fluoro-5-methyl-2,4-hexadiene, 2-methoxycarbonyl-5-methyl-2,4-hexadiene, 1,1 •difluoro-4-methyl-1,3"pentadiene, 1, l"dichloro-4-methyl-1,3-pentadiene, 2"methyl-2,4-hexadie»e, 2,3-dimethyl-2-pentene, l,l,l-tR1chloro-4-methyl-3-pentene and the like. 1, l-dibromo-4-methyl- 1,3-pehtadienG, l-chloro-l-fluoro-4"methyll,3-pentadiene, l-fluoro-l-bromo-4"methyl-l,3"pentadinene, 2-(l,l,l,3,3,3"hexafluoroisopropoxycarbonyl)-5-methyl-2,4-hexadiene, 1- methoxy4-methyM, 3-pentadiene, l-ethoxy"4-methyM,3-pentadiene, l-propoxy"4"methyl-l,3-pentadiene, I"fluoro- l-mBthoxy-4methyl- 1,3-pentadiene, l-fluoro- l-ethoxy4-methyl- 1,3-pentadiene, l-fluoro-l"propoxy"4"methyM,3-pentadiene, lJ,l"tR1bromo-4-methyl-3"pentene, 2-bromo-2,2-dimethyl-4-hexene, 2chloro"2,5-dimethyl-4-hexene, l-methoxy-2-methyl" 1 -propene, lethoxy-2-methyl-l-propene, l-propoxy2-methyM-propene, l-methoxy-8-methyl-2-butene, l-ethoxy-3"methyl2-butene, lpropoxy-3-inethyl-2-butene, l,l-diinethox5"-3methyl"2-butene, 1, l"diethoxy-3-methyl"2-butene, isopropylidenecyclopropane, isopropylidenecyclobutane, isopropylidenecyclopentane and the like. Examples of the alkyl group having 1 to 8 carbon atoms R6pR6sented by R? m formula (4) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n"octyl group and the like. Examples of the cycloalkyl group which may be optionally substituted with a lower alkyl group include a cyclohexjd group, a 1-menthyl group, a d-menthyl group. Examples of the phenyl or benzyl group which may be optionally substituted with a lower alkyl group, a lower alkoxy group or a phenoxy group R6pR6sented by R7 in formula (4) include a phenyl group, a 2-methylphenyl group, a 3,5"dimethylphenyl group, a 4-methyl-2,6-di-tert-butylphenyl group, a 2-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a benzyl group, a 3-phenoxybenz>"l group and the like. Examples of the lower alkyl group which may be pR6sent on the cycloalkyl group or on the phenyl group include a (Cl-C4)alkyl group such as a methyl group, an ethyl group, a n-propyl group, an i"propyl group, a n-butyl group, an ibutjd group, a sec-butyl group, and a t"butyl group. Examples of the lower alkoxy group which may be pR6sent on the phenyl group include a (Cl"C4)alkoxyl group such as a methoxy group, an ethoxy group, a npropoxy group, an i-propoxy group, a n-butoxy group, an ibutoxy group, a secbutoxy group, and a t-butoxy group. PR6ferR6d aR6 a (Cl-C6)alkyl group, a cyclohexyl group, a Imenthyl group, a d-menthyl group, a phenyl group, a 2-methjdphen34 group, a 3,5-diR3ethylphenyl group, a 4-methyl-2,6-di-tert-butylphenyl group, a 2-methoxyphenyl group, a 3,5-dimethoxyphenyl group and a 3-phenoxybenzj"l group. Specific examples of the diazoacetic acid ester of formula (4) include ethyl dia2oacetate, n-propyl diazoacetate, tertbutyl diazoacetate, phenyl diazoacetate, l-menthyl diazoacetate, cyclohexyl diazoacetate and the like. Said diazoacetic esteR3 of formula (4) is commercially available or may be pR6paR6d by the known method such as a method of R6acting corR6sponding amino acid esteR3 with a diazotizing agent such as sodium nitR1te and mineR3l acids may be used. The R6action of prochiR3l olefin of formula (3) with diazoacetic esteR3 of formX1la (4) in the pR6sence of the pR6paR6d copper complex catalyst composition is usually performed by adding the diazoacetic ester of formula (4) to a mixtuR6 of the copper complex catalyst composition and the prochiR3l olefin (3) and optionally in a solvent. The pR6sent R6action may be performed in the pR6sence of a R6ducing agent such as phenylhydR3zine or the like. An amount of prochiR3l olefins of formula (3) to be used is usually 1 mole or moR6 per mol of the diazoacetic esteR3 of formula (4). The upper limit theR6of is not particularly limited and, for example, a large excess amount may be used so as to serve as a R6action solvent. An amount of the copper complex catalyst to be used is usually 0.001 to 1 mole %, pR6feR3bly 0,002 to 0.5 mole % in terms of copper R6lative to diazoacetic esteR3 of formula (4). Examples of the solvent to be used include a halogenated hydrocarbon such as 1,2-dihloroethane, chloroform, carbon tetR3chloR1de or the like, an aliphatic hydrocarbon such as hexane, heptane, cyclohexane and the like. an aromatic hydrocarbon such as benzene, toluene, xylene and the like, an ester such as methyl acetate, ethyl acetate and the Uke, and a mixtuR6 theR6of. Alternatively, prochiR3l olefin (3) may be used as a solvent. An amount of the solvent to be used is usually 2 to 50 parts by weight, pR6feR3bly 3 to 30 parts by weight per 1 part by weight of the diazoacetic ester (4). A R6action tempeR3tuR6 is usually 5 to 150oC, pR6feR3bly 10 to 120o"C. In addition, the R6action is usually performed under an inert gas atmospheR6 such as a nitrogen gas or the like. After completion of the R6action, the optically active cyclopropanecarboxylic acid ester deR1vative of formula (2) can be sepaR3ted by distillation or the like, which may be subjected to ester hydrolysis or the like, or may be further puR1fied, for example, by distillation, column chromatogR3phy or the like, if necessary. Examples of the optically active cyclopropanecarboxylic acid esteR3 of formula (2) include optically active methyl 2-methylcyclopropanecarboxylate, ethyl 2-methylcyclopropanecarboxylate, n-propy 1 2 - methy ley clop rop anecarboxy late, isopropyl 2-methylcyclopropanecarboxylate, isobutyl2-methylcyclopropanecai:boxylate, tert-butyl 2-methylcyclopropanecarboxylate, cyclohexyl2-methylcyclopropanecarboxylate, menthyl 2"methylcyclopropanecarboxylate, 4-methyl-2,6-di-tert-butylphenyl 2-methylcyclopropanecarboxylate, inethyl2,2-dimethylcyclopropanecarboxylate, ethyl 2,2-dimethylcyclopropanecarboxylate, n-propyl 2,2-dimethylcyclopropanecarboxylate, isopropyl 2,2"dimethylcyclopropan6carboxylate, isobutyl 2,2dimethylcyclopropanecarboxylate, tert-butyl 2,2"dim6thylcyclopropanecarboxylate, cyclohexyl, 2,2- dimethylcyclopropanecarboxs"late, menthyl 2,2dimethylc3"clopropanecarboxylate, methyl 2,2,3-tR1methylcyclopropanecarboxylate, ethyl 2,2,3-tR1methylcyclopropanecarboxy late, npropyl 2,2,3"tR1methylcyclopropanecarboxylate, isopropyl 2,2,3-ti"imethylcyclopropanecarboxylate, isobutyl 2,2,3 "tR1methylcyclopropanecarboxylate, tert"butyl 2,2,3-tR1methylcyclopropanecarboxylate, cyclohexyl, 2,2,3"tR1methylcyclopropanecarboxylate, menthyl 2,2,3"tR1methylcyclopropanecarboxylate, 4methyl-2,6-di-tert-butylphenyl2,2-dimethylcyclopropanecarboxylate, methyl 2,2-dimethyl"3-(2"methyl-l-propenyl)cyclopropanecai"boxylate, ethyl 2,2-dimet.hyl-3-(2"methyl-l-propenyl)cyclopropanecarboxylate, npropyl 2,2-dimethyl-3"(2"methyl-l-propenyl)cyclopropan6carboxylate, isopropyl 2,2-dimethyl-3-(2"methyl-l-propenyDcyclopropanecaiboxylate, isobutyl 2,2dinietyl"3-(3"methyl-lpropenyDcyclopropanecarboxylate, tertbutyl 2,2-dimethyl-3"(2"methyM-propenyl)cyclopropanecai"boxylate, cyclohexyl 2,2-dimethyl-3-(2-methyM-propenyDcyclopropanecarboxylate, menthyl 2,2-dimethyl-3"(2-methyM-propenyDcyclopropanecarboxylate, (4-methyl-2,6-di-tert-butylphenyD 2,2-dimethyl- 3- (2-methyl" l-propenyOcyclopropanecarboxylate, methyl 2,2- dimethyl - 3-(2,2-dichloro" 1 -ethenyDcycloprop anecarboxylate, ethyl 2,2-dimethyl-3"(2,2-dichloro-l-etheny0cyclopropanecarboxylate, n-propyl 2,2-diinethyl-3(2,2-dichloro-l"ethenyl)cyclopropanecarboxylate, isopropyl 2,2-dimethyl"3-(2,2dichloro-l"ethenyl)cyclopropan6carboxylate, isobutyl 2,2-dimethyl-3-(2,2"dichloro-l-ethenyl)cyclopropanecarboxylate, tert"butyl 2,2"dimethyl-3(2,2"dichloro-l"ethenyl)cyclopropanecarboxylate, cyclohexyl 2,2"dimethyl-3(2,2-dichloro"l-ethenyDcyclopropanecarboxylate, menthyl 2,2"diinethyl-3 (2,2"dichloro-l-ethenyl)cyclopropanecarboxylate, (4-methyl-2,6-di"tertbutylphenyl)2,2-diR3ethyl-3-(2,2-dichIoro"l- ethenyDoyclopropanecarboxj"late, methyl 2,2"dimethyl-3"(2,2,2-trtchloroethyl)cyclopropanecarboxylate, ethyl 2,2-dimethyl-3-(2,2,2-tR1chloroet.hyl)cyclopropanecarboxylate, n-prop5"l 2,2-dimethyl-3-(2,2,2-tR1chloroethyl)cyclopropanecarboxylate, isopi"opyl 2,2"dimethyl"3-(2,2,2-tR1chloroethyl)cyclopropanecarboxylate. isobuM 2,2-dimethyl-3"(2,2,2-tR1chloroethyl)cyclopropanecarboxylate, uert"butyl 2,2-dimethyl-3(2,2,2-tR1chloroethyl)cyclopropanecarboxylate, cyclohexyl 2,2-dimethyl-3-(2,2,2"tR1chloroethyDcyclopropanecarboxylate, menthyl2,2-dimethyl-3-{2,2,2-tR1chloroethyl)cyclopi"opanecarboxylate, 4-methyl-2,6-di-tert-butylphenyl 2,2-dimethyl-3-(2,2,2"tR1chloroethyl)cyclopropanecarboxylate and the like. The optically active salicylideneaminoalcohol compound of formula (1) contained in the R6sidue after isolating the optically active cyclopropanecarboxylic acid ester deR1vative of formula (2) can be R6coveR6d by subjecting the R6sidue to crystallization tR6atment, column chromatogR3phy or the like. The optically active salicylideneaminoalcohol compound of formula (l) can be obtained, for example, by R6acting an optically active amino alcohol of formula (5)" wheR6in R1 and R3 have the same meaning s as defined above, with a fealicylaldehyde deR1vative of formula (6)" wheR6in Si and X2 aR6 the same as defined above. The optically active amino alcohol compound of formula (5) to be used in this process include those having R1 and R2 groups as specified above and specific examples theR6of include optically active 2amino-1,1-diphenyl- 1-propanol, 2-amino-1,1 • di(2" methoxyphenyl) ■ l-propanol, 2amino-l,l-di(2-i60propoxyphenyl)-l-propanol, 2-amino-l,ldi(2butoxy"5-t-butylphenyl)-l"propanol, 2-amino-l,ldiphenyl-3-phenyl-l-propanol, 2-amino-l,l 2-amino-l,l-di(2-isopropoxyphenyl)-3-phenyM-propanol, 2-amino-l,l-di(2-butoxy-5-t-butylphenyl)-3-phenyl-lpropanol, 2-amino-l,l-di(2-methoxyphe)ayl)-3-phenyl-l-butanol, 2-amino"l,l-di(2"butoxy-5-t-butylphenyl)-l-propanol, 2-amino-l,l-di(2-octyloxy5-t-butylphenyD"l"propanol, 2-amino-1, l-di(2-butoxy"5-t-butylphenyl)-3phGnyM-propanol, 2-amino-l,l-di(2-methoxyphenyl)-l-propanol, 2-amino-l,l-di(2-beivzyloxy5 inethyIphenyl)"3-(4-isopropoxyphenyl)-l- propanol, 2-amino-1, l-di(2-mGthoxyphen.yD-3-methyl-Ibutanol, 2"aR3ino-3-phenyl-l-propanol, 2-amino-l,ldi(2"t-butyl-4-methylphenyl)-3-phenyI"l-propanol, 2amino-l,l-di(4-t-but>"lphenyl)l-propanol, 2-amino-l,l-di(2-methoxyphenyl)-3-methyl-l-propanol and the like. The R6action of the optically active amino alcohol (5) with the salicylaldehyde deR1vative (6) is usually conducted at room tempeR3tuR6 to the boiling point of the solvent used. Said R6action is usually conducted by contacting the optically active amino alcohol (5) with the slicylaldehyde deR1vative (6) in an organic solvent, examples of which include an aromatic hydrocarbon solvent svich as toluene, xylene or the like, a halogenated hydrocarbon solvent such as chlorobenzene, dichloroethane or the like and an alcohol solvent such as methanol, ethanol or the like and a mixtuR6 theR6of. An amount theR6of to be used is not particularly limited. An amount of the slicylaldehyde deR1vative to be used is usually 0.8 to 1.5 moles, pR6feR3bly 0.9 to 1.2 moles per R3ol of the optically active amino alcohol of formula (5). The R6action may be conducted under dehydR3ting water which is produced duR1ng the R6action. Examples The pR6sent invention will be illustR3ted by way of the following Examples but aR6 not to be construed to limit the pR6sent invention theR6to. The yield and the optical puR1ty weR6 calculated according to the following equations. Yield (%)=BX100/A optical puR1ty of obtained cyclopropanecarboxylate ■ (+)"tR3n8 e.e.% =(C-D)X100/X(C+D) (+)-cis e.e.% =(EF) X 100/(E+F) provided that, A=employed diazoacetic ester (mol) B=cyclopropanecarboxylic ester (moD produced after the R6action C=(+)"tR3ns isomer D=(-)-tR3ns"i!somer E=(+)-cis-isomer F=(-)"cis-isomer R6feR6nce Example 1 0.968 g (2.0 mmol) of {R)-2"aniino-l,l-di(2-butoxy5"t-butj"lpheny0-propanol and 0.244g (2.0 mmol) of salicylaldehyde weR6 dissolved in 20 ml of ethanol and 20 ml of toluene, the solution was heated at R6flux for 1 hour. The solvent was distilled off from the R6action mixtuR6 and dR1ed to obtain 1.17 g of (R)-N-salicyliden-2-amino-l,l-di(2-butoxy-5-t-butylphenyl)-propanol as a yellow solid. Example 1 After a glass Schlenk tube having an inner volume of 50 ml was purged with nitrogen, 58.8 mg(0.1 mmol) of (R)N-salicyliden-2-amino"l,l-di(2-butOxy5-t-but3^1phenyl)-propanol obtained in R6feR6nce Example 1 and a 5% solution of 63.5 mg(containing 0.05 mg-atom Cu) of copper naphthenate in toluene weR6 dissolved in 25 ml of dr>" toluene at room tempeR3t\u:e for 1 hoiu", 19.3 mg of 28% sodium methylate in methanol was added, and the mixtuR6 was stirR6d at room tempeR3tuR6 for 1 hour to pR6paR6 a complex catalyst solution. A stirR6r was placed in a Schlenk tube having an inner volume of 100 ml, the tube was purged with a niti-ogen gas, and 5 ml (Cu 0.01 mg-atom) of the complex catalyst pR6paR6d above was added theR6in. Next, after 30 g (273 mmol) of 2,5"dimethyl-2,4-hexadiene was added, 1.1 mg (O.Ol mmol) of phenylhydR3zine was added. TheR6after, the Schlenk tube was warmed to 80oC, and 10 ml of a solution of ethyl diazoacetate in toluene (containing ethyl diazoacetate:20 mmol) was added theR6to over 2 houR3. After the addition, the mixtuR6 was kept at 80oC for 30 minutes, cooled to a room tempeR3tuR6 and the yield of the product of chi-ysanthemic acid ester and the isomer R3tio of tR3ns/cia weR6 analyzed by Gas chromatogR3phy, and the optical puR1ty was analyzed by high-performance liquid chromatogi-aphy. The yield of chrysanthemic acid ethyl ester was 90.1% based on ethyl diazoacetate employed, tR3ns/cis was 55/45, and optical puR1ty was 71%e.e.(tR3ns) and 60%e.e.(cis). Examples 2 to 16 Optically active Salicylideneaminoalcohol compounds weR6 synthesized from optically active aminoalcohols and salicylaldehyde deR1vatives as in R6feR6nce Example 1. The R6sults aR6 summaR1zed in Table 1, and the complex catalyst solutions weR6 pR6paR6d using optically active salicylideneaminoalcohol compound, copper naphthenate and sodium methylato as shown in Table 1. The cyclopropanation R6action was performed using the chiR3l copper complex catalyst compositions shown in Table 2 as in Example 1. Example 17 Optically active Salicylideneaminoalcohol compound weR6 synthesized from optically active aminoalcohols and salicylaldehyde deR1vatives as in R6feR6nce Example 1 To a 100 ml Schlenk, 0.2 mmol of (R)-N-(5"nitrosalicylidene)-2-amino-l,l"di(2-butoxy-5"t-butylphenyl)"l-propan ol weR6 added 35.9 mg(0.18 mmol) of copper acetate monohydR3te and 50 ml of toluene, and the R6sulting mixtuR6 was R6acted for 1 hour under stirR1ng at 80oC. The R6action mixtuR6 was cooled to a room tempeR3tuR6, and an aqueous solution of 40 mg of sodium hydroX1de dissolved in 30 ml of water was added theR6to. The mixtuR6 was tR3nsferR6d to a sepaR3tory funnel, and was thoroughly stirR6d, settled and the sepaR3ted aqueous layer was R6moved. 10 ml of water was added theR6to, stirR6d again and settled. The oily layer was tR3nsferR6d to a Schlenk tube and azeotropically dehydR3ted under heating to give the product. The product was diluted with toluene to make a 50 ml toluene solution of the optically active copper complex catalyst mixtuR6. To a 100 ml Schlenk tube purged with nitrogen weR6 added 1 ml of the optically active copper complex catalyst solution pR6paR6d above and the same starting mateR1al as used in Example 1, and the R6sulting mixtuR6 was R6acted according to the same manner as in Example 1. The R6sults aR6 shown in Table 2. Example 18 A chiR3l copper complex was pR6paR6d according to the similar manner as in Example 17 except that the aalicylideneaminoalcohol compound obtained in Example 6 weR6 used. Ethyl cyclopropanecarboxylate deR1vative was produced with the chiR3l copper complex. The R6sults aR6 shown in Table 2. Example 19 10 ml (Cu 0.02 mg-atom) of the copper complex catalyst solution pR6paR6d in Example 1 was added to an stainless autoclave with 100 mlvolume purged with nitrogen gas befoR6hand. 2.2 mg (0.02 mmol )of phenylhydR3zine and 4.5 g (80.4 mmol) of isobutylene weR6 added theR6to. Then the R6action mixtuR6 was heated to 40 oC, and 10 ml of ethyl diazoacetate (20 mmoD in toluene weR6 added theR6to over 2 hR3 with a pump. TheR6after the R6action mixtuR6 was kept at 40o"C for IhouR3, and then cooled to a room tempeR3tuR6. Yield of the ethyl cyclopropane-carboxylate was analyzed by gaschoromatogR3phy. The optical puR1ty of the product was determined by deR1vatizing the product to l-menthylate ester theR6of. Yield 91% (vs. ethyl diazoacetate), Optical puR1ty- 81% e.e. Example 20 Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10ml of the copper complex catalyst pR6paR6d in Example 4. The R6sults aR6 shown in Table 2. Example 21 Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10 ml of the copper complex catalyst pR6paR6d in Example 5. The R6sults aR6 shown in Table 2. Example 22 To a 100 ml Schlenk tube, weR6 added 0.2 mmol of (R)-N-salicylidene-2-ainino-1, ldi(2-butoxy-S-t-butylphenyl) l-propanol, 35.9 mg(0.18 mmol) of copper acetate monohydR3te and 50 ml of toluene, and the R6sulting mixtuR6 was R6acted for 1 hoiir under stirR1ng at SO"C. The R6action mixtuR6 was cooled to a room tempeR3tuR6, and an aqueous solution of 40 mg of sodium hydroX1de dissolved in 30 ml of distilled water was added theR6to. The mixtuR6 was tR3nsferR6d to a sepaR3tory funnel, and was thoroughly stirR6d, settled and the sepaR3ted aqueous layer was R6moved. 10 ml of distilled water was added theR6to and stirR6d again. After aettled, the oily layer was tR3nsferR6d to a Schlenk tube, a condensing tube equipped with a sepaR3tory tube amovinted theR6on, the R6action solution was azeotropically dehydR3ted under heating to give the catalyst composition. Toluene was added to make a 50 ml toluene solution of the optically active copper complex catalyst. Ethyl cydopropanecarboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10ml of the copper complex catalyst pR6paR6d above was used . The R6sults aR6 shown in Table 2. Example 23 Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 2.5 ml of the copper complex catalyst solution pR6paR6d in Example 2 weR6 used. Yield: 91% (based on the ethyl diazoacetate), Optical puR1ty: 86 % e.e. Example 24 Ethyl cyclopropane-carboxhlate deR1vative was produced according to a similar manner aft in Example 19 except that 2.5 ml of the copper complex catalyst pR6paR6d in Example 12 weR6 used. Yield: 92%, Optical Purity"- 87% e.e. Example 25 An optically active Salicylideneaminoalcohol compound weR6 synthesized from optically active aminoalcohole and salicylaldehyde deR1vatives as in Example 2. After a glass Schlenk tube having an inner volume of 50 ml was purged with nitrogen, 16.4 mg(0.0259 mmoD of (,R)-N-(5-nitorosalicyliden)"2-aminol,l-di(2-butoxy5-tbutylphenyl)"l-propanol obtained in Example 2 and a 5% solution of 29.8mg(containing 0.0235 mg-atom Cu) of copper naphthenate in toluene weR6 dissolved in 13 ml of dry ethyl acetate satuR3ted with a nitrogen gas at room tempeR3tuR6 for 1 hour to pR6paR6 a complex catalyst solution. Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 1 except that 4 ml of the copper complex catalyst solution pR6paR6d weR6 used. The yield of chrysanthemic acid ethyl ester was 89.2% R6lative to employed ethyl diazoacetate, tR3ns/cis was 54/46, and optical puR1ty was 66%e.e.(tR3ns) and 46%e.e.(cis). Example 26 A chiR3l copper complex pR6paR6d according to the similar manner as in Example 25 except that the (R)"N-(5-nitorosalicyliden)-2-amino" l,l-di(2-methox5"phenyl)-l-propanol was used in place of (R)-N-(o-nitorosalicyliden)-2-amino-l,l-di(2-butoxy5tbutylphenyD-l" propanol. Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 1. The yield of chrysanthemic acid ethyl ester was 90.9% R6lative to employed ethyl diazoacetate, tR3ns/cis was 59/41, and optical puR1ty was 55%e.e.(tR3ns) and 47%c.e.(cis). Properties of n-salicylideneaminoalcohoU obtaiaed by examples aR6 shown below, m.p.measuR6d by automatical melting point meaatiR1ng appaR3tus maaufactuR6d by Metier®. 6 Values of "H-NMR (CDCI3, TMS) aR6 given below. 2: (R)N-(5nitro8alicylidene)-2-an)ino-l,l-di(2butoxy-5-t-butyiphenyl>-l-propanoI 3: (R)-N-(3-florosalicylidene)-2-Hmmo-l,l-di(2-butoxy-5-t-butylphenyD-l-propajaol "1 • 0.86-1.57 (m. 35H), 3.66-3.77 (m, 4H). 4.95 (s, IH), 5.34 (s, IH). 6.4-8.01 (m, IIH). in.p.51.9""c 6- (R)-N-(5-nitroBalicylideae)-2-aniino"l,l-diphenyl-rpropaDol (5 : i.34-1.36 (d, 3H), 2.59 (s, IH). 4.64-4.66 (q, IH), 6.82-6.9 (m, iH), 7.2-7.54 (m, IIH), 8.12-8.15 (m, 2h), 8.26 (s, Ih) in.p.208.3°c T- (R)-N{3-liuoro8alicylidene)-2-anunol,l-dipbenyll-propanol fl : 1.271.29 (d. 3H), 2.58 (s, IH), 4.54-4.61 (q. IH), 6.7-7.54 (m, 14H), 8.34 (s, IH). m.p.lOO""c 8= (R)-N-(3-bromosalicylidene)-2-amuio-l,l"diphenyl-l-propanol 5 : 1.25-1.27 (d. 3H), 2.56 (s, IH), 4.55-4.62 (q, IH), 6.76-6.91 (d, IH), 7.15-7.54 (m, 13H), 8.28 (s, IH). m.p.l73°c 9: (R)-N-(3,5-dibTOmosalicylidene)-2-aniino-l.l-diphenyl-l-propanol (5 : 1.28-1.30 (d, 3H), 2.59 (s, IH), 4.524.59 (q, IH), 7.1-7.66 lO: (S)-N-(5-nitrosaUcylidene)-2-ainiao-l,l-di(2-b€nzyloxy5-methylphcnyJ)-3-(4-isopropoxyphenyl)-l-propatiol 6 ■■ 1.26-1.31 (q, 6H), 1.94 (s, 3H), 2.13 (s, 3H), 2.87-2.91 (d, 2H), 4.424.50 (m, IH), 4.82-4.95 (m, 4H), 5.86 (s, IH), 6.59-8.02 (m,26H) II" (S)-N-(3-fluoroaalicyLideiie)2-amino-l,l-di(2-benzyloxy-5-methylphenyl)-3-(4-isopropoxyphenyl)-l-propanoI (5: 1 27-1.31 (t, 6H), 1.94 (s, 3H), 2.11 (s, 3H), 2.91-2.94 (m, 2H), 4.42-4.50 (m. IH), 4.77-4.92 (m, 4H). 5.67 (s, IH), 6.31-7.39 (m,26H). R3.p.82.7°c 12: (R)-N-(5-iutrosalicylidenc)-2-amino-l,l-di(2-butoxy-5-t-biitylpiienyl)-3-phenyl-l-propano] (J : 0.91-1.57 (m, 34H), 3.78-3.96 (m, 4H), 5.05 (s, IH), 5.75 (s, IH), 6.62-8.57 (m, I6H). oil 13: (R)-N(311uorosalicylidenc>-2-ainino-l,l"di(2-butoxy-5-tbutylplienyl)-3-phenyM-propaiiol 6 :"0.87-1.56 (m, 34H}, 3.71-3.97 (m, 4H), 4.85 (s, IH), 5.75 (s. IH), 6.62-8.57 (m, 16H). oil 14: (R)-N-(5-nitrosalkyliclene)-2-animo-l,l-diphenyl-3-phenyM-propanoL in.p.202°c 15a (R)-N-(3fluornsalic}"lidcne)-2-amiiio-l,l-diphenyl-3-phenyI-l-propaiiol m.p.lSD.S"c IG- (S)-N-(5-nitrosalicylidene)-2-amino-l,l-di(2-metlioxypheiiyl)-3-methyM-butano] iii.p.ll8.7°c 17: (S)-N-(3-fluorocalicylid8ne)-2-ainmo-l,l-di(2-aiethoxypheayl)-3-methyl-l-butanol m.p.79.6°c WE CLAIM: 1. A chiral copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of formula (1): wherein R1 represents an alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group and cycloalkoxy group, an aralkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, and a cycloalkoxy group, R2 represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group, X1 and X2 are the same or different and independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group, and two adjacent X1 and X2 together with the benzene ring to which they are bonded may form a l-hydroxy-2- or 2-hydroxy-l-naphthyl group, and the carbon atom denoted by " " is an asymmetric carbon atom having either an S or R configuration, and with a mono-valent or di-valent copper compound in an inert solvent, the amount of the mono-valent or di¬valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1). 2. A process for producing an optically active cyclopropane-carboxylic acid ester of formula (2): wherein R3, R4, R5 and R6 are as defined below and R7 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group which may be optionally substituted with a lower alkyl group, a benzyl group or phenyl group which may be optionally substituted with a lower alkyl group, a lower alkoxy group or a phenoxy group, which comprises the steps of preparing a chiral copper complex catalyst composition as claimed in claim 1 by: (a) contacting an optically active N-salicylideneaminoalcohol compound of formula (1): with a mono-valent or di-valent copper compound, in an inert solvent, wherein R1 represents an alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group, and cycloalkoxy group, an aralkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group, R2 represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group, X1 and X2 are the same or different and independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group and two adjacent X1 and X2 together with the benzene ring to which they are bonded may form a l-hydroxy-2- or 2-hydroxy-l-naphthyl group, and the carbon atom denoted by " * " is an asymmetric carbon atom having either an S or R configuration, and with a mono-valent or di-valent copper compound, in an inert solvent, the amount of the mono-valent or di¬valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and (b) reacting a prochiral olefin of formula (3): wherein R3, R4, R5 and R6 independently represent a hydrogen atom, a halogen atom, a (Cl-C10)alkyl group which may be substituted with a halogen atom or a lower alkoxy group, a (C4-C8)cycloalkyl group, an aryl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, R3 and R4, or R5 and R6 may be bonded at their terminals to form an alkylene group having 2-4 carbon atoms, and one of R3, R4, R5 and Re groups represents an alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy carbonyl group, of which alkoxy may be substituted with a halogen atom or atoms, provided that when R3 and R5 are the same, R4 and R6 are not the same, with a diazoacetic acid ester of formula (4): N2CHCO2R7 (4) wherein R? is the same as defined above, in the presence of a chiral copper complex catalyst composition so produced in step (a). 3. A chiral copper complex catalyst composition, substantially as hereinabove described and exemplified.

Full Text

The prsent invention R6lates to a production process for asymmetR1c synthesis of cyclopropane-carboxylic acid compound using a chiR3l copper complex catalyst.
As a process for producing an optically active cyclopropanecarboxylic acid
ester deR1vative, theR6 has been R6ported a process of using a chiR3l copper complex
catalyst which was pR6paR6d by R6acting equivalent or excess amount of cupR1c salt
with optically active salicylideneaminoalcohol (JP-B 53-43955, JP-A 50-151842, JP-
A 54-73758 and JP-A 59-225194).
However, in the disclosed processes said copper complex R6quiR6d puR1fication by R6crystallization or washing with methanol or the like to R6move an excessive amount of copper compound.
According to the pR6sent invention, a chiR3l copper complex catalyst composition can be obtained in an industR1ally advantageously and can be used in an asymmmetR1c cyclopropanation R6action with good R6producibility.
Our co-pending application 63/MAS/2001 R6lates to "An optically active saUcylideneaminoalcohol compound".
The pR6sent invention provides a chiR3l copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of formula (1):

with a mono-valent or di-valent copper compound in an inert solvent, wheR6in R1 R6pR6sents an alkyl group which may be substituted with a group selected from an alkoxy group, an aR3lkyloxy group, an aryloxy group, and cycloalkoxy group, an aR3lkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aR3lkyloxy group, an aryloxy group, and a cycloalkoxy group,
R2 R6pR6sent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aR3lkyl or
phenyl group which may be substituted with a group selected from an alkyl group, an
alkoxy group, an aR3lkyloxy group, an aryloxy group, and a cycloalkoxy group,
X1 and X2 aR6 the same or diffeR6nt and independently R6pR6sent a hydrogen atom, a
halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group, and
two adjacent X1 and X2 together with the benzene R1ng to which they aR6 bonded may
form a l-hydroxy-2- or 2,-hydroxy-l-naphthyl group, and the carbon atom denoted by
" * " is an asymmetR1c carbon atom having either an S or R configuR3tion, and the
amount of the mono-valent or di-valent copper compound is less than 1 mole per 1
mole of the optically active N-salicylideneaminoalcohol compound of formula (1),
and a process for producing an optically active .

cyclopropanecarboxylic acid ester of formula (2)"

wheR6in R3, R4, R5 and R6 aR6 as defined below, and R7 R6pR6sents
an alkyl group having I to 8 carbon atoms,
a cycloalkyl group which may be optionally substituted with a lower alkyl group,
a benzyl group or phenyl group which may be optionally substituted with a lower alkj"l group, a lower alkoxy group or a phenoxy group, which compR1ses the steps of
(a) contacting an optically active N-salicylideneaminoalcohol
compound of formula (!):

with a mono"valent or di-valenl copper compound in an inert solvent,
wheR6in R1, R2, X1, X2 and " * " have the same meanings as defined above, and the amount of the monovalent or di-valent copper compound is h?ss than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (l), and
(b) R6acting a prochiR3l olefin of formula (3)"

wheR6in R3, R4. R5 and R6 independently R6pR6sent a hydrogen atom, a halogen atom,
a (Cl-C10)alkyl group which may be substituted with a halogen atom or a lower alkoxy group,
a (C4-C8)cycloalkyl group,
an aryl group which may be substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group,
R3 and R4, or R5 and R6 may be bonded at their terminals to form an alkylene group having 2-4 carbon atoms, and
one of R2, R4, R5 and R6 groups R6pR6sents an alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy carbonyl group, of which alkoxy may be substituted with a halogen atom or atoms
provided that when R3 and R6 aR6 the same, R4 and R6 aR6 not the same, with a diazoacetic acid ester of formula (4):
N2CHCO2R7 (4)
wheR6in R7 is the same as defined above, in the pR6sence of
a chiR3l copper complex catalyst composition so produced in step (a).
Detailed DescR1ption
FiR3t, a descR1ption will be made to the optically active salicylideneaminoalcohol compound of formula (l) as defined above.

Examples of the alkyl group which may be substituted with a group selected from an alkoxy group, an aR3lkyloxy group, an aryloxy group and a c3"cloalkoxy group, R6pR6sented by R1, include
a (Cl-C8)alkyl group (e.g., a methyl, ethyl, n-propyl, i-propyl, n-butyl. rbutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-pentyl, n-octyl, n-nonyl, or n-decyl group) which may be substituted with a group selected from
a (Cl-C4)alkoxy group(e.g., a methoxy, ethoxy, n-propoxy,
i-propoxy, n-butoxy, i-butoxy, secbutoxy or t"butoxy group),
a (C7-Cll)aR3lkyIoxy group(e.g., a benzyloxy or naphthylmethyloxy group),
a (C6-Cll)aryloxy groupCe.g., a phenoxy or naphthoxy group), a (C4-C6)cycloalkoxy groupCe.g., a cyclobutyloxy, cyclopentyloxy or cyclohexyloxy group) and the like.
Examples of the aR3lkyl group, the aryl group and the cycloalkyl group, all of which may be sub.stituted with a group selected from an alkyl group, an alkoxy group, an aR3lkyloxy group, an aryloxy group and a cycloalkoxy group include
a (C7-Cll)aR3lkyl groupCe.g., a benzyl, or naphthylmethyl group),
a (C6-C10)aryl groupCe.g., a phenyl, or naphthyl group),
a (C4"C6)cycloalkyl groupCe.g., a cyclobutyl, cyclopentyl, or cyciohexyl group), all of which may be substituted with
the CCl-C8)alkyl, CC7-Cll)aR3lkyloxy, CCB-ClDaryloxy and
(C4-C6)cycloalkoxy group as specified above and a CClC8)alkoxy
groupCe.g, , a methoxy, ethoxy, n-propoxy, i-propoxy, nbutoxy,
ibutoxy, sec-butoxy, t-butoxy, n-pentoxy, nhexyloxy, npentyloxy or
n-octyloxy group).
The alkyl group R6pR6sented by R2 include said (Cl-C8)alkyl group as above. The cycloalkyl group R6pR6sented by R2 include said (C4-C6)cycloalkyl group ae above.
The aR3lkyl or phenyl group which may be substituted with a group

selected from an alkyl group, an alkoxy group, an aR3lkj"loxy group, an aryloxy group and a cydoalkoxy group R6pR6sented by R2 include the same meanings as defined above for the groups R6pR6sented by R1
The subetituent group X1 and X2 of the salicylideneaminoalcohol compound of formvila (l) will be explained below.
Exampleis of the halogen atom R6pR6sented by X1 and X2 include a fluoR1ne atom, a chloR1ne atom and a bromine atom.
Examples of the alkj"l group include a (Cl-CS) alkyl group such as a methyl, ethyl, npropyl, i"propyl, n"butyl, tbntyl, sec-butyl, n-pentyl, nhexyl, n-heptyl, n-octyl and the like.
Examples of the alkoxy group include the same (Cl-C4)alkoxy group as defined above in the alkoxy group for R1
In salicylideneaminoalcohol compound of formula (1), pR6ferR6d aR6
a salicylideneaminoalcohol compound (1) in which X1 R6pR6sents a bromine atom and X2 is a hydrogen atom or a bromine atom,
a salicyhdeneaminoalcohol compound (1) in which X1 R6pR6sents a nitro group and X2 is a hydrogen atom, a methjd group or a methoxy group,
a salicylideneaminoalcohol compound (l) in which X1 R6pR6sents a chloR1ne atom and X2 is a chloR1ne atom, and
a salicylideneaminoalcohol compound (l) in which X1 is a hydrogen atom and X2 is a fluoR1ne atom.
MoR6 pR6ferR6d aR6
a salicylideneaminoalcohol compound (l) in which X1 R6pR6sents a nitro group or a bromine atom and X2 is a hydrogen atom,
a salicylidenGammoalcohol compound (1) in which X1 R6pR6sents a chloR1ne atom and X2 is a chloR1ne atom, and
a salicylideneaminoalcohol compound (1) in which X1 is a hydrogen atom and X2 is a fluoR1ne atom.
Among the optically active salicylideneaminoalcohol compound of formula (1), R1 is pR6feR3bly an alkyl group having 1 to 6 carbon atoms, an

aR3lkyl, an aryl group, and R3 is pR6feR3bly an alkyl group (e.g. lower alkyl groups having 1 to 6 carbon atoms), an aR3lkyl group (e.g., a benzyl group), an aryl group (e.g., a phenyl group, a 2-methoxyphenyl group, a 2 tert-butoxy-5-tert-butylphenyl group or a 2"OCtyloxy"5-t6rt-butylphenyl group).
Specific examples the optically active salicylideneaminoalcohol compound of formula (l) include optically active N-salicyliden"2-ainino-l,l"diphenyM-propanol, i^-aalicyliden-2-amino-l,l-di(2-methoxyphenyl)-l-propanol, N-salicyliden-2aminO"l,l"di(2"isopropoxyphenyl)"l-propanol, N-6alicyUden-2"amino-1, l-di(2butoxy-S-t-butj"lphenyl)- l-propanol, N-salicyliden-2"amino"l,l-diphenyl"3-phenyM"propanol, N-salicyliden-2*amino" 1, l-di(2"methoxyphenyl)"3-phenyl- 1-propanol, N-salicyliden-2-amino-l,l-di(2isopropoxyphenyl)-3-phenyM"propanol, N"salicyliden-2"amino-l,l"di(2-butoxy-6-t-butylpbenyl)-3"phGnyl"l-propanol, N"8alicyliden-2-amino-l,l-di(2 methoxyphenyl)"3-phenyM-butanol, N"(3 fluorosalicyliden)-2-aminol,l"di(2-butoxy-5-t*butylphenyl)-l"propanol, N"(3 fluoro8alicyliden)-2-aR3ino-l,l-di(2-octyloxy-5-t-butylphenyl)"l-propanol, N(3-fluorosalicj"liden)-2"amino-l,l"di(2-butoxy5-t-butylphenyD-3"phenyM-propanol,
N-(3-fluorosalicyUden)-2-amino*l,ldi(2-m6thoxj"plienyl)-l-propanol, N-(3-fluoro8alicyUden)-2-amino" 1,1 ■diphenyM"propanol, N-(3"fluorosalicyliden)-2-aminO"l,ldi(2"benzyloxy-5-methylphenyl)"3-(4-iso-propoxyphenyi)-Ipropanol,
N-(3-fluoro8alicyliden)-2-aminol,l"diphenyl-3"phenyM-propanol, N-(3fluorosalicyliden)-2-amino"l,l"di(2"methoxyphenyl)"3"methyM"butanol, N-(3-fluorosaliq"liden)-2-amino-3-phenyMpropanol, N (3,5-dichlorosalicylidene)-2amino-l,l"diphenylpropanol, N"(3.5-dichlorosalicylidene)-2-amino*l,l-di-(2-R3ethoxyphenyDpropanol N"-(3.5-dichlorosalicylidene)-2-amino-l,l-di(5"tert-butyl-2-tert-butoxyphenyl)-

3-phenyl- Ipropanol,
N-(3,5-dichlorosalicylidene)-2-amiiiO"l,l-di"(5-terfbutyl-2 octyloxyphenyl)-
propanol
N-(5-bromosalicyliden)-2-amino-l.l"diphenyl-l-propanol,
N"(5-bromosalicyliden)-2-ammo-l,l-di(2-methoxypheiiyl)"l-propanoI,
N-(3,5-dibroinosalicyUden)-2-ainino"l,l-diphenyl-l-pi"opanol,
N(5-nitrosalicyliden)"2"amino-l,l-diph6nyM-propanol,
N-(5-nitrosalicyliden)-2-ammo-l,l"diphenyl-3-phenyM-propanol,
N"(5-nitroBalicyliden)"2-ainino-l.l-di(2-butoxy5"t-butylplienyl)-3-phenyl-
propanol,
N-(5-nitrosalicyliden)-2"aminoX,l"di(2-benzyloxy5-methylphenyl)-3-(4-i80-
propoxjTphenyl) ■ 1 -propanol,
N-(5nitroaalicyliden)-2-amino*l,l-di(2-methoxyphenyl)"l-propanol,
N-(5-nitrosalicyliden)"2-amino-1, l-di(2-t-b utyl-4-methylphenyl)-3-phenyM*
propanol,
N-(5-nitrosalicyliden)-2-amino-l,l-di(2-butoxy5-t-butylphenyl)-l-propanol,
N"(5-nitrosalicyliden)-2-amino"l,l-di(2*methoxyphenyl)-3-xnethyMbutanol,
N-(5"nitro8alicylidene)"2-amino"l,l-dr(5-tert"butyl-2"octyoxyphenyl)l"
propanol,
N (5-nitro8alicylidene)"2-ajaino-l,l-di(5-tert-butyl-2-tert-butoxyph6nyl)-3-
phenyl" 1-propanol,
N-(3-methoxy-5-mtrosalicyliden)-2-ainino-l,l-di(2"butoxy-5-t"butylph6nyl )-1-
propanol,
N-(3-methoxy5-nitrosaIicylideu)-2"aR3ino"l,l-di(2"methoxyphenyl)"l-
propanol,
N-(3-methoxy 5-mtrosalicyliden)"2-amino- 1,1-diphenyl ■ 1-propanol,
N-(3"t-butylsalicyliden)*2-aniino-l,l"diphenyM-propanoI,
N"(3,5-drtbutylsalicyliden)*2-amino-l,l-di(2-methoxyphenyl)-l-propanol,
and the like. Said optically active compounda may have either an S
configuR3tion or R configuR3tion with R6spect to the carbon atom denoted by"

* " in the formula above.
The salicylidenaminoalcohol of formula (l) is usually contacted with a mono"valent or di-valent copper compound to produce a chiR3l copper complex in an inert solvent.
Examples of the mono-valent or di-valent copper compound include
a copper salt of an organic carboxylic acid having 2 to 15 carbon atoms such as copper acetate, copper naphthenate, copper octanoate and the like, and a copper salt such as copper chloR1de, copper bromide, copper nitR3te, copper sulfate, copper methanesulfonte, copper tR1fluoromethanesulfonate, copper cyanate, copper carbonate and copper oX1de, and a mixtuR6 theR6of.
Examples of the inert solvent include a hydrocarbon such as hexane, heptane, cyclohexane or the like, an ester such as methyl acetate, ethyl acetate, ethyl propionate or the like, a ketone such as acetone, methyl ethyl ketone or the like, a halogenated hydiocarbon such as butyl chloR1de, dichloroethane, chloroform, carbon tetR3chloR1de or the like, and an aromatic hydrocarbon such as toluene, xylene or the like. The mixtuR6 of solvent descR1bed above can be also used. An amount theR6of to be used is not particularly limited. ProchiR3l olefins of formula (3) to be used in the next cyclopropanation step may also be used as a solvent.
An amount of the copper compound to be used is less than 1 mole, usually 0.2 to 0.95 mole, pR6feR3bly 0.4 to 0.94 mole per mol of the optically active salicylideneaminoalcohol compound of fonnula (1). The R6action tetopeR3tuR6 is usually room tempeR3tuR6 to the boiling point of the solvent used, or typically 10 to 100°C.
The R6action mixtuR6, which is the pR6sent chiR3l copper complex catalyst composition, can be used as it is for the asymmetR1c synthesis, or it may be concentR3ted to a suitable concentR3tion, if necessary. The chiR3l copper catalyst composition thus obtained usually contains 0,1 to 30 (wt)% of the chiR3l copper complex which is deR1ved from the slicylideneamiuoalcohol compound of formula (1) and the copper compound, and the inert solvent. It

can also be used after the isolation by R6moving the solvent.
Alternatively, the R6sulting R6action mixtuR6 may be further contacted with a base, if necessary.
Examples of the base include
an alkali metal alcoholate such as sodium methylate and sodium ethylate, which can be used as they are as powdeR3 or as a solution in alcohol such as methanol, ethanol or the like,
alkali metal hydroX1de such as sodium hydroX1de, potassium hydroX1de or the like,
alkali metal carbonate or bicarbonate such as sodium carbonate, sodium bicarbonate and the like. These aR6 usually used as an aqueous solution.
The amount of the base to be used is usually 0.1-8 moles, pR6feR3bly around 0.5-3 moles per mole of the copper compound.
Although the R6sulting R6action mixtuR6 can be used as it is without R6movmg a salt produced by neutR3lization of them (for example, sodium acetate in the case of using copper acetate, sodiiun naphthenate in the case of using copper naphthenate), it is pR6feR3bly used after R6moving the salt by washing with water. In this case, the catalyst may be used after being dehydR3ted.
Thus obtained chiR3l copper complex catalyst composition in a solution form, of which concentR3tion is usually within the R3nge of the concentR3tion as descR1bed above, optionally adjusted by concentR3tion or addition of an appropR1ate solvent, can be used in the cyclopropanation R6action, hence a puR1fying step is not particularly necessary. Although the product can be isolated by R6moving the solvent, the solution is usually used as it is and, theR6foR6, the pR6sent catalyst composition is suitably used in a continuous R6action process because of R6ady feeding of catalyst.
Although the structuR6 of an asymmetR1c copper complex catalyst obtained heR6in is not always clearly established, it shows pR3ctically good

activity for an industR1al production process.
Next, a descR1ption will be made to the step of producing optically active cyclopropane-carboxylic acid ester of formula (2) as defined above, which step compR1sing R6acting a prochiR3l olefin of formula (3) with a diazoacetic acid ester of formula (4) in the pR6sence of a chiR3l copper complex catalyst composition so produced.
R3, R4, R3 or R6 of the prochiR3l olefin of formula (3) will be explained below.
Examples of the alkyl group which may be substituted with a halogen atom or an alkoxy group include
a linear or bR3nched alkyl group having 1 to 10 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n"decyl group,
an alkyl group substituted with a halogen atom such as a fluoR1ne atom, a chloR1ne atom, a bromine atom and the like a haloalkyl group such as a chloromethyl, dichloromethyl, tR1chloromethyl, difluoromethyl, tR1fluoromethyl, 2,2,2-tR1chloroethyl group or the like,
an alkyl group substituted with an alkoxy group such as a methoxy, ethoxy, n-propoxy, ipropoxy group or the like.
Examples of the alkylene group formed by R3 and R4, or R5 and R6 include ah alkylene group having 2 to 4 carbon atoms such as dimethylnene, tR1methylene, or tetR3methylene group.
Examples of the alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy cax"bonyl group, of which alkoxy may be substituted with a halogen atom or atoms, R6pR6sented by R3, R4, R3 include
a linear or bR3nched alkenyl groups having 1 to 10 carbon atoms such as an ethenyl, propenyl, 2-methylpropenyl, 1-butenyl, 2-butenyl, or hexenyl group,
a haloalkenyl group, which is the above"descR1bed alkenyl group

substituted with the above-descR1bed halogen atom or atoms, such as a chloroethenyl group, a chloropropenyl group, 2,2-dicshlor6ethenyl group, 2,2-difluoroethenyl group or the like,
an alkoxy(Cl-C3)carbonyl substituted alkenyl group such as 2-methoxycarbonyl"2-methylethenyl group,
2*(1,1,1,3,3,3"hexafluoroisopropoxycarbonyl)-1-methylethenyl group or the like.
Specific examples of the prochiR3l olefin (3) include propene, l"butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 4-chloro-l-butene, 2"pentene, 2-heptene, 2"methyl"2-butene, 2,5"dimethyl"2,4-hexadiene, 2"chloro-5-methyl-2,4"hexadiene, 2-fluoro-5"methyl*2,4"hGxadiene, l,l,l-tR1fluoro-5-methyl-2,4-hexadiene, 2-methoxycarbonyl-5-methyl-2,4-hexadiene,
1,1 •difluoro-4-methyl-1,3"pentadiene, 1, l"dichloro-4-methyl-1,3-pentadiene, 2"methyl-2,4-hexadie»e, 2,3-dimethyl-2-pentene, l,l,l-tR1chloro-4-methyl-3-pentene and the like. 1, l-dibromo-4-methyl- 1,3-pehtadienG, l-chloro-l-fluoro-4"methyll,3-pentadiene, l-fluoro-l-bromo-4"methyl-l,3"pentadinene,
2-(l,l,l,3,3,3"hexafluoroisopropoxycarbonyl)-5-methyl-2,4-hexadiene, 1- methoxy4-methyM, 3-pentadiene, l-ethoxy"4-methyM,3-pentadiene, l-propoxy"4"methyl-l,3-pentadiene, I"fluoro- l-mBthoxy-4methyl- 1,3-pentadiene, l-fluoro- l-ethoxy4-methyl- 1,3-pentadiene, l-fluoro-l"propoxy"4"methyM,3-pentadiene,
lJ,l"tR1bromo-4-methyl-3"pentene, 2-bromo-2,2-dimethyl-4-hexene, 2chloro"2,5-dimethyl-4-hexene, l-methoxy-2-methyl" 1 -propene, l*ethoxy-2-methyl-l-propene, l-propoxy2-methyM-propene, l-methoxy-8-methyl-2-butene, l-ethoxy-3"methyl*2-butene,

lpropoxy-3-inethyl-2-butene, l,l-diinethox5"-3methyl"2-butene, 1, l"diethoxy-3-methyl"2-butene, isopropylidenecyclopropane, isopropylidenecyclobutane, isopropylidenecyclopentane and the like.
Examples of the alkyl group having 1 to 8 carbon atoms R6pR6sented by R? m formula (4) include
a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n"octyl group and the like.
Examples of the cycloalkyl group which may be optionally substituted with a lower alkyl group include a cyclohexjd group, a 1-menthyl group, a d-menthyl group.
Examples of the phenyl or benzyl group which may be optionally
substituted with a lower alkyl group, a lower alkoxy group or a phenoxy
group R6pR6sented by R7 in formula (4) include a phenyl group, a
2-methylphenyl group, a 3,5"dimethylphenyl group, a
4-methyl-2,6-di-tert-butylphenyl group, a 2-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a benzyl group, a 3-phenoxybenz>"l group and the like.
Examples of the lower alkyl group which may be pR6sent on the cycloalkyl group or on the phenyl group include a (Cl-C4)alkyl group such as a methyl group, an ethyl group, a n-propyl group, an i"propyl group, a n-butyl group, an ibutjd group, a sec-butyl group, and a t"butyl group.
Examples of the lower alkoxy group which may be pR6sent on the phenyl group include a (Cl"C4)alkoxyl group such as a methoxy group, an ethoxy group, a npropoxy group, an i-propoxy group, a n-butoxy group, an ibutoxy group, a secbutoxy group, and a t-butoxy group.
PR6ferR6d aR6 a (Cl-C6)alkyl group, a cyclohexyl group, a Imenthyl group, a d-menthyl group, a phenyl group, a 2-methjdphen34 group, a 3,5-diR3ethylphenyl group, a 4-methyl-2,6-di-tert-butylphenyl group, a 2-methoxyphenyl group, a 3,5-dimethoxyphenyl group and a 3-phenoxybenzj"l

group.
Specific examples of the diazoacetic acid ester of formula (4) include ethyl dia2oacetate, n-propyl diazoacetate, tertbutyl diazoacetate, phenyl diazoacetate, l-menthyl diazoacetate, cyclohexyl diazoacetate and the like.
Said diazoacetic esteR3 of formula (4) is commercially available or may be pR6paR6d by the known method such as a method of R6acting corR6sponding amino acid esteR3 with a diazotizing agent such as sodium nitR1te and mineR3l acids may be used.
The R6action of prochiR3l olefin of formula (3) with diazoacetic esteR3 of formX1la (4) in the pR6sence of the pR6paR6d copper complex catalyst composition is usually performed by adding the diazoacetic ester of formula (4) to a mixtuR6 of the copper complex catalyst composition and the prochiR3l olefin (3) and optionally in a solvent. The pR6sent R6action may be performed in the pR6sence of a R6ducing agent such as phenylhydR3zine or the like.
An amount of prochiR3l olefins of formula (3) to be used is usually 1 mole or moR6 per mol of the diazoacetic esteR3 of formula (4). The upper limit theR6of is not particularly limited and, for example, a large excess amount may be used so as to serve as a R6action solvent.
An amount of the copper complex catalyst to be used is usually 0.001 to 1 mole %, pR6feR3bly 0,002 to 0.5 mole % in terms of copper R6lative to diazoacetic esteR3 of formula (4).
Examples of the solvent to be used include a halogenated hydrocarbon such as 1,2-dihloroethane, chloroform, carbon tetR3chloR1de or the like,
an aliphatic hydrocarbon such as hexane, heptane, cyclohexane and the like.
an aromatic hydrocarbon such as benzene, toluene, xylene and the like,
an ester such as methyl acetate, ethyl acetate and the Uke, and a mixtuR6 theR6of. Alternatively, prochiR3l olefin (3) may be used as a solvent.

An amount of the solvent to be used is usually 2 to 50 parts by weight, pR6feR3bly 3 to 30 parts by weight per 1 part by weight of the diazoacetic ester (4).
A R6action tempeR3tuR6 is usually 5 to 150oC, pR6feR3bly 10 to 120o"C. In addition, the R6action is usually performed under an inert gas atmospheR6 such as a nitrogen gas or the like.
After completion of the R6action, the optically active cyclopropanecarboxylic acid ester deR1vative of formula (2) can be sepaR3ted by distillation or the like, which may be subjected to ester hydrolysis or the like, or may be further puR1fied, for example, by distillation, column chromatogR3phy or the like, if necessary.
Examples of the optically active cyclopropanecarboxylic acid esteR3 of formula (2) include optically active methyl 2-methylcyclopropanecarboxylate, ethyl 2-methylcyclopropanecarboxylate, n-propy 1 2 - methy ley clop rop anecarboxy late, isopropyl 2-methylcyclopropanecarboxylate, isobutyl2-methylcyclopropanecai:boxylate, tert-butyl 2-methylcyclopropanecarboxylate, cyclohexyl2-methylcyclopropanecarboxylate, menthyl 2"methylcyclopropanecarboxylate,
4-methyl-2,6-di-tert-butylphenyl 2-methylcyclopropanecarboxylate, inethyl2,2-dimethylcyclopropanecarboxylate, ethyl 2,2-dimethylcyclopropanecarboxylate, n-propyl 2,2-dimethylcyclopropanecarboxylate, isopropyl 2,2"dimethylcyclopropan6carboxylate, isobutyl 2,2dimethylcyclopropanecarboxylate, tert-butyl 2,2"dim6thylcyclopropanecarboxylate, cyclohexyl, 2,2- dimethylcyclopropanecarboxs"late, menthyl 2,2*dimethylc3"clopropanecarboxylate,

methyl 2,2,3-tR1methylcyclopropanecarboxylate,
ethyl 2,2,3-tR1methylcyclopropanecarboxy late,
npropyl 2,2,3"tR1methylcyclopropanecarboxylate,
isopropyl 2,2,3-ti"imethylcyclopropanecarboxylate,
isobutyl 2,2,3 "tR1methylcyclopropanecarboxylate,
tert"butyl 2,2,3-tR1methylcyclopropanecarboxylate,
cyclohexyl, 2,2,3"tR1methylcyclopropanecarboxylate,
menthyl 2,2,3"tR1methylcyclopropanecarboxylate,
4*methyl-2,6-di-tert-butylphenyl2,2-dimethylcyclopropanecarboxylate,
methyl 2,2-dimethyl"3-(2"methyl-l-propenyl)cyclopropanecai"boxylate,
ethyl 2,2-dimet.hyl-3-(2"methyl-l-propenyl)cyclopropanecarboxylate,
npropyl 2,2-dimethyl-3"(2"methyl-l-propenyl)cyclopropan6carboxylate,
isopropyl 2,2-dimethyl-3-(2"methyl-l-propenyDcyclopropanecaiboxylate,
isobutyl 2,2dinietyl"3-(3"methyl-lpropenyDcyclopropanecarboxylate,
tertbutyl 2,2-dimethyl-3"(2"methyM-propenyl)cyclopropanecai"boxylate,
cyclohexyl 2,2-dimethyl-3-(2-methyM-propenyDcyclopropanecarboxylate,
menthyl 2,2-dimethyl-3"(2-methyM-propenyDcyclopropanecarboxylate,
(4-methyl-2,6-di-tert-butylphenyD
2,2-dimethyl- 3- (2-methyl" l-propenyOcyclopropanecarboxylate,
methyl 2,2- dimethyl - 3-(2,2-dichloro" 1 -ethenyDcycloprop anecarboxylate,
ethyl 2,2-dimethyl-3"(2,2-dichloro-l-etheny0cyclopropanecarboxylate,
n-propyl 2,2-diinethyl-3*(2,2-dichloro-l"ethenyl)cyclopropanecarboxylate,
isopropyl 2,2-dimethyl"3-(2,2dichloro-l"ethenyl)cyclopropan6carboxylate,
isobutyl 2,2-dimethyl-3-(2,2"dichloro-l-ethenyl)cyclopropanecarboxylate,
tert"butyl 2,2"dimethyl-3(2,2"dichloro-l"ethenyl)cyclopropanecarboxylate,
cyclohexyl 2,2"dimethyl-3*(2,2-dichloro"l-ethenyDcyclopropanecarboxylate,
menthyl 2,2"diinethyl-3 (2,2"dichloro-l-ethenyl)cyclopropanecarboxylate,
(4-methyl-2,6-di"tertbutylphenyl)2,2-diR3ethyl-3-(2,2-dichIoro"l-
ethenyDoyclopropanecarboxj"late,
methyl 2,2"dimethyl-3"(2,2,2-trtchloroethyl)cyclopropanecarboxylate,

ethyl 2,2-dimethyl-3-(2,2,2-tR1chloroet.hyl)cyclopropanecarboxylate,
n-prop5"l 2,2-dimethyl-3-(2,2,2-tR1chloroethyl)cyclopropanecarboxylate,
isopi"opyl 2,2"dimethyl"3-(2,2,2-tR1chloroethyl)cyclopropanecarboxylate.
isobuM 2,2-dimethyl-3"(2,2,2-tR1chloroethyl)cyclopropanecarboxylate,
uert"butyl 2,2-dimethyl-3(2,2,2-tR1chloroethyl)cyclopropanecarboxylate,
cyclohexyl 2,2-dimethyl-3-(2,2,2"tR1chloroethyDcyclopropanecarboxylate,
menthyl2,2-dimethyl-3-{2,2,2-tR1chloroethyl)cyclopi"opanecarboxylate,
4-methyl-2,6-di-tert-butylphenyl
2,2-dimethyl-3-(2,2,2"tR1chloroethyl)cyclopropanecarboxylate and the like.
The optically active salicylideneaminoalcohol compound of formula (1) contained in the R6sidue after isolating the optically active cyclopropanecarboxylic acid ester deR1vative of formula (2) can be R6coveR6d by subjecting the R6sidue to crystallization tR6atment, column chromatogR3phy or the like.
The optically active salicylideneaminoalcohol compound of formula (l) can be obtained, for example, by R6acting an optically active amino alcohol of formula (5)"

wheR6in R1 and R3 have the same meaning s as defined above, with a fealicylaldehyde deR1vative of formula (6)"

wheR6in Si and X2 aR6 the same as defined above.
The optically active amino alcohol compound of formula (5) to be used

in this process include those having R1 and R2 groups as specified above and
specific examples theR6of include optically active
2amino-1,1-diphenyl- 1-propanol,
2-amino-1,1 • di(2" methoxyphenyl) ■ l-propanol,
2*amino-l,l-di(2-i60propoxyphenyl)-l-propanol,
2-amino-l,ldi(2butoxy"5-t-butylphenyl)-l"propanol,
2-amino-l,ldiphenyl-3-phenyl-l-propanol,
2-amino-l,l* 2-amino-l,l-di(2-isopropoxyphenyl)-3-phenyM-propanol,
2-amino-l,l-di(2-butoxy-5-t-butylphenyl)-3-phenyl-lpropanol,
2-amino-l,l-di(2-methoxyphe)ayl)-3-phenyl-l-butanol,
2-amino"l,l-di(2"butoxy-5-t-butylphenyl)-l-propanol,
2-amino-l,l-di(2-octyloxy5-t-butylphenyD"l"propanol,
2-amino-1, l-di(2-butoxy"5-t-butylphenyl)-3phGnyM-propanol,
2-amino-l,l-di(2-methoxyphenyl)-l-propanol,
2-amino-l,l-di(2-beivzyloxy5 inethyIphenyl)"3-(4-isopropoxyphenyl)-l-
propanol,
2-amino-1, l-di(2-mGthoxyphen.yD-3-methyl-Ibutanol,
2"aR3ino-3-phenyl-l-propanol,
2-amino-l,l*di(2"t-butyl-4-methylphenyl)-3-phenyI"l-propanol,
2amino-l,l-di(4-t-but>"lphenyl)l-propanol,
2-amino-l,l-di(2-methoxyphenyl)-3-methyl-l-propanol and the like.
The R6action of the optically active amino alcohol (5) with the salicylaldehyde deR1vative (6) is usually conducted at room tempeR3tuR6 to the boiling point of the solvent used.
Said R6action is usually conducted by contacting the optically active amino alcohol (5) with the slicylaldehyde deR1vative (6) in an organic solvent, examples of which include an aromatic hydrocarbon solvent svich as toluene, xylene or the like, a halogenated hydrocarbon solvent such as chlorobenzene, dichloroethane or the like and an alcohol solvent such as methanol, ethanol

or the like and a mixtuR6 theR6of. An amount theR6of to be used is not particularly limited.
An amount of the slicylaldehyde deR1vative to be used is usually 0.8 to 1.5 moles, pR6feR3bly 0.9 to 1.2 moles per R3ol of the optically active amino alcohol of formula (5). The R6action may be conducted under dehydR3ting water which is produced duR1ng the R6action.
Examples
The pR6sent invention will be illustR3ted by way of the following Examples but aR6 not to be construed to limit the pR6sent invention theR6to.
The yield and the optical puR1ty weR6 calculated according to the following equations.
Yield (%)=BX100/A
optical puR1ty of obtained cyclopropanecarboxylate ■
(+)"tR3n8 e.e.% =(C-D)X100/X(C+D)
(+)-cis e.e.% =(EF) X 100/(E+F) provided that,
A=employed diazoacetic ester (mol)
B=cyclopropanecarboxylic ester (moD produced after the R6action C=(+)"tR3ns isomer D=(-)-tR3ns"i!somer E=(+)-cis-isomer F=(-)"cis-isomer
R6feR6nce Example 1
0.968 g (2.0 mmol) of
{R)-2"aniino-l,l-di(2-butoxy5"t-butj"lpheny0-propanol and 0.244g (2.0 mmol)

of salicylaldehyde weR6 dissolved in 20 ml of ethanol and 20 ml of toluene, the solution was heated at R6flux for 1 hour. The solvent was distilled off from the R6action mixtuR6 and dR1ed to obtain 1.17 g of
(R)-N-salicyliden-2-amino-l,l-di(2-butoxy-5-t-butylphenyl)-propanol as a yellow solid.
Example 1
After a glass Schlenk tube having an inner volume of 50 ml was
purged with nitrogen, 58.8 mg(0.1 mmol) of
(R)N-salicyliden-2-amino"l,l-di(2-butOxy5-t-but3^1phenyl)-propanol obtained in R6feR6nce Example 1 and a 5% solution of 63.5 mg(containing 0.05 mg-atom Cu) of copper naphthenate in toluene weR6 dissolved in 25 ml of dr>" toluene at room tempeR3t\u:e for 1 hoiu", 19.3 mg of 28% sodium methylate in methanol was added, and the mixtuR6 was stirR6d at room tempeR3tuR6 for 1 hour to pR6paR6 a complex catalyst solution.
A stirR6r was placed in a Schlenk tube having an inner volume of 100 ml, the tube was purged with a niti-ogen gas, and 5 ml (Cu 0.01 mg-atom) of the complex catalyst pR6paR6d above was added theR6in. Next, after 30 g (273 mmol) of 2,5"dimethyl-2,4-hexadiene was added, 1.1 mg (O.Ol mmol) of phenylhydR3zine was added. TheR6after, the Schlenk tube was warmed to 80oC, and 10 ml of a solution of ethyl diazoacetate in toluene (containing ethyl diazoacetate:20 mmol) was added theR6to over 2 houR3. After the addition, the mixtuR6 was kept at 80oC for 30 minutes, cooled to a room tempeR3tuR6 and the yield of the product of chi-ysanthemic acid ester and the isomer R3tio of tR3ns/cia weR6 analyzed by Gas chromatogR3phy, and the optical puR1ty was analyzed by high-performance liquid chromatogi-aphy. The yield of chrysanthemic acid ethyl ester was 90.1% based on ethyl diazoacetate employed, tR3ns/cis was 55/45, and optical puR1ty was 71%e.e.(tR3ns) and 60%e.e.(cis).

Examples 2 to 16
Optically active Salicylideneaminoalcohol compounds weR6 synthesized from optically active aminoalcohols and salicylaldehyde deR1vatives as in R6feR6nce Example 1. The R6sults aR6 summaR1zed in Table 1, and the complex catalyst solutions weR6 pR6paR6d using optically active salicylideneaminoalcohol compound, copper naphthenate and sodium methylato as shown in Table 1.
The cyclopropanation R6action was performed using the chiR3l copper complex catalyst compositions shown in Table 2 as in Example 1.
Example 17
Optically active Salicylideneaminoalcohol compound weR6 synthesized from optically active aminoalcohols and salicylaldehyde deR1vatives as in R6feR6nce Example 1
To a 100 ml Schlenk, 0.2 mmol of
(R)-N-(5"nitrosalicylidene)-2-amino-l,l"di(2-butoxy-5"t-butylphenyl)"l-propan ol weR6 added 35.9 mg(0.18 mmol) of copper acetate monohydR3te and 50 ml of toluene, and the R6sulting mixtuR6 was R6acted for 1 hour under stirR1ng at 80oC. The R6action mixtuR6 was cooled to a room tempeR3tuR6, and an aqueous solution of 40 mg of sodium hydroX1de dissolved in 30 ml of water was added theR6to. The mixtuR6 was tR3nsferR6d to a sepaR3tory funnel, and was thoroughly stirR6d, settled and the sepaR3ted aqueous layer was R6moved. 10 ml of water was added theR6to, stirR6d again and settled. The oily layer was tR3nsferR6d to a Schlenk tube and azeotropically dehydR3ted under heating to give the product. The product was diluted with toluene to make a 50 ml toluene solution of the optically active copper complex catalyst mixtuR6.
To a 100 ml Schlenk tube purged with nitrogen weR6 added 1 ml of the optically active copper complex catalyst solution pR6paR6d above and the same starting mateR1al as used in Example 1, and the R6sulting mixtuR6 was R6acted according to the same manner as in Example 1. The R6sults aR6

shown in Table 2.
Example 18
A chiR3l copper complex was pR6paR6d according to the similar manner as in Example 17 except that the aalicylideneaminoalcohol compound obtained in Example 6 weR6 used. Ethyl cyclopropanecarboxylate deR1vative was produced with the chiR3l copper complex. The R6sults aR6 shown in Table 2.
Example 19
10 ml (Cu 0.02 mg-atom) of the copper complex catalyst solution pR6paR6d in Example 1 was added to an stainless autoclave with 100 mlvolume purged with nitrogen gas befoR6hand. 2.2 mg (0.02 mmol )of phenylhydR3zine and 4.5 g (80.4 mmol) of isobutylene weR6 added theR6to. Then the R6action mixtuR6 was heated to 40 oC, and 10 ml of ethyl diazoacetate (20 mmoD in toluene weR6 added theR6to over 2 hR3 with a pump. TheR6after the R6action mixtuR6 was kept at 40o"C for IhouR3, and then cooled to a room tempeR3tuR6. Yield of the ethyl cyclopropane-carboxylate was analyzed by gaschoromatogR3phy. The optical puR1ty of the product was determined by deR1vatizing the product to l-menthylate ester theR6of. Yield 91% (vs. ethyl diazoacetate), Optical puR1ty- 81% e.e.
Example 20
Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10ml of the copper complex catalyst pR6paR6d in Example 4. The R6sults aR6 shown in Table 2.
Example 21
Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10 ml of the copper complex

catalyst pR6paR6d in Example 5. The R6sults aR6 shown in Table 2.
Example 22
To a 100 ml Schlenk tube, weR6 added 0.2 mmol of (R)-N-salicylidene-2-ainino-1, ldi(2-butoxy-S-t-butylphenyl) l-propanol, 35.9 mg(0.18 mmol) of copper acetate monohydR3te and 50 ml of toluene, and the R6sulting mixtuR6 was R6acted for 1 hoiir under stirR1ng at SO"C. The R6action mixtuR6 was cooled to a room tempeR3tuR6, and an aqueous solution of 40 mg of sodium hydroX1de dissolved in 30 ml of distilled water was added theR6to. The mixtuR6 was tR3nsferR6d to a sepaR3tory funnel, and was thoroughly stirR6d, settled and the sepaR3ted aqueous layer was R6moved. 10 ml of distilled water was added theR6to and stirR6d again. After aettled, the oily layer was tR3nsferR6d to a Schlenk tube, a condensing tube equipped with a sepaR3tory tube amovinted theR6on, the R6action solution was azeotropically dehydR3ted under heating to give the catalyst composition. Toluene was added to make a 50 ml toluene solution of the optically active copper complex catalyst.
Ethyl cydopropanecarboxylate deR1vative was produced according to a similar manner as in Example 19 except that 10ml of the copper complex catalyst pR6paR6d above was used . The R6sults aR6 shown in Table 2.
Example 23
Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 19 except that 2.5 ml of the copper complex catalyst solution pR6paR6d in Example 2 weR6 used. Yield: 91% (based on the ethyl diazoacetate), Optical puR1ty: 86 % e.e.
Example 24
Ethyl cyclopropane-carboxhlate deR1vative was produced according to a similar manner aft in Example 19 except that 2.5 ml of the copper complex

catalyst pR6paR6d in Example 12 weR6 used. Yield: 92%, Optical Purity"- 87% e.e.
Example 25
An optically active Salicylideneaminoalcohol compound weR6 synthesized from optically active aminoalcohole and salicylaldehyde deR1vatives as in Example 2.
After a glass Schlenk tube having an inner volume of 50 ml was
purged with nitrogen, 16.4 mg(0.0259 mmoD of
(,R)-N-(5-nitorosalicyliden)"2-aminol,l-di(2-butoxy5-tbutylphenyl)"l-propanol obtained in Example 2 and a 5% solution of 29.8mg(containing 0.0235 mg-atom Cu) of copper naphthenate in toluene weR6 dissolved in 13 ml of dry ethyl acetate satuR3ted with a nitrogen gas at room tempeR3tuR6 for 1 hour to pR6paR6 a complex catalyst solution.
Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 1 except that 4 ml of the copper complex catalyst solution pR6paR6d weR6 used. The yield of chrysanthemic acid ethyl ester was 89.2% R6lative to employed ethyl diazoacetate, tR3ns/cis was 54/46, and optical puR1ty was 66%e.e.(tR3ns) and 46%e.e.(cis).
Example 26
A chiR3l copper complex pR6paR6d according to the similar manner as in Example 25 except that the (R)"N-(5-nitorosalicyliden)-2-amino" l,l-di(2-methox5"phenyl)-l-propanol was used in place of (R)-N-(o-nitorosalicyliden)-2-amino-l,l-di(2-butoxy5tbutylphenyD-l" propanol.
Ethyl cyclopropane-carboxylate deR1vative was produced according to a similar manner as in Example 1. The yield of chrysanthemic acid ethyl ester was 90.9% R6lative to employed ethyl diazoacetate, tR3ns/cis was 59/41, and optical puR1ty was 55%e.e.(tR3ns) and 47%c.e.(cis).

Properties of n-salicylideneaminoalcohoU obtaiaed by examples aR6 shown below, m.p.measuR6d by automatical melting point meaatiR1ng appaR3tus maaufactuR6d by Metier®. 6 Values of "H-NMR (CDCI3, TMS) aR6 given below.
2: (R)N-(5nitro8alicylidene)-2-an)ino-l,l-di(2butoxy-5-t-butyiphenyl>-l-propanoI
3: (R)-N-(3-florosalicylidene)-2-Hmmo-l,l-di(2-butoxy-5-t-butylphenyD-l-propajaol "1 • 0.86-1.57 (m. 35H), 3.66-3.77 (m, 4H). 4.95 (s, IH), 5.34 (s, IH). 6.4-8.01 (m, IIH). in.p.51.9""c

6- (R)-N-(5-nitroBalicylideae)-2-aniino"l,l-diphenyl-rpropaDol
(5 : i.34-1.36 (d, 3H), 2.59 (s, IH). 4.64-4.66 (q, IH), 6.82-6.9 (m, iH), 7.2-7.54 (m, IIH), 8.12-8.15 (m, 2h), 8.26 (s, Ih)
in.p.208.3°c
T- (R)-N{3-liuoro8alicylidene)-2-anunol,l-dipbenyll-propanol
fl : 1.271.29 (d. 3H), 2.58 (s, IH), 4.54-4.61 (q. IH), 6.7-7.54 (m, 14H), 8.34 (s, IH). m.p.lOO""c
8= (R)-N-(3-bromosalicylidene)-2-amuio-l,l"diphenyl-l-propanol
5 : 1.25-1.27 (d. 3H), 2.56 (s, IH), 4.55-4.62 (q, IH), 6.76-6.91 (d, IH), 7.15-7.54 (m, 13H), 8.28 (s, IH). m.p.l73°c
9: (R)-N-(3,5-dibTOmosalicylidene)-2-aniino-l.l-diphenyl-l-propanol
(5 : 1.28-1.30 (d, 3H), 2.59 (s, IH), 4.524.59 (q, IH), 7.1-7.66 lO: (S)-N-(5-nitrosaUcylidene)-2-ainiao-l,l-di(2-b€nzyloxy5-methylphcnyJ)-3-(4-isopropoxyphenyl)-l-propatiol
6 ■■ 1.26-1.31 (q, 6H), 1.94 (s, 3H), 2.13 (s, 3H), 2.87-2.91 (d, 2H), 4.424.50 (m, IH), 4.82-4.95 (m, 4H), 5.86 (s, IH),
6.59-8.02 (m,26H)
II" (S)-N-(3-fluoroaalicyLideiie)2-amino-l,l-di(2-benzyloxy-5-methylphenyl)-3-(4-isopropoxyphenyl)-l-propanoI (5: 1 27-1.31 (t, 6H), 1.94 (s, 3H), 2.11 (s, 3H), 2.91-2.94 (m, 2H), 4.42-4.50 (m. IH), 4.77-4.92 (m, 4H). 5.67 (s, IH), 6.31-7.39 (m,26H). R3.p.82.7°c
12: (R)-N-(5-iutrosalicylidenc)-2-amino-l,l-di(2-butoxy-5-t-biitylpiienyl)-3-phenyl-l-propano] (J : 0.91-1.57 (m, 34H), 3.78-3.96 (m, 4H), 5.05 (s, IH), 5.75 (s, IH), 6.62-8.57 (m, I6H). oil

13: (R)-N(311uorosalicylidenc>-2-ainino-l,l"di(2-butoxy-5-tbutylplienyl)-3-phenyM-propaiiol 6 :"0.87-1.56 (m, 34H}, 3.71-3.97 (m, 4H), 4.85 (s, IH), 5.75 (s. IH), 6.62-8.57 (m, 16H). oil
14: (R)-N-(5-nitrosalkyliclene)-2-animo-l,l-diphenyl-3-phenyM-propanoL in.p.202°c
15a (R)-N-(3fluornsalic}"lidcne)-2-amiiio-l,l-diphenyl-3-phenyI-l-propaiiol m.p.lSD.S"c
IG- (S)-N-(5-nitrosalicylidene)-2-amino-l,l-di(2-metlioxypheiiyl)-3-methyM-butano] iii.p.ll8.7°c
17: (S)-N-(3-fluorocalicylid8ne)-2-ainmo-l,l-di(2-aiethoxypheayl)-3-methyl-l-butanol m.p.79.6°c

WE CLAIM:
1. A chiral copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of formula (1):

wherein R1 represents an alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group and cycloalkoxy group, an aralkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, and a cycloalkoxy group, R2 represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group,
X1 and X2 are the same or different and independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group, and two adjacent X1 and X2 together with the benzene ring to which they are bonded may form a l-hydroxy-2- or 2-hydroxy-l-naphthyl group, and the carbon atom denoted by " * " is an asymmetric carbon atom having either an S or R configuration, and with a mono-valent or di-valent copper compound in an inert solvent, the amount of the mono-valent or di¬valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1).

2. A process for producing an optically active cyclopropane-carboxylic acid ester of formula (2):

wherein R3, R4, R5 and R6 are as defined below and R7 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group which may be optionally substituted with a lower alkyl group, a benzyl group or phenyl group which may be optionally substituted with a lower alkyl group, a lower alkoxy group or a phenoxy group, which comprises the steps of preparing a chiral copper complex catalyst composition as claimed in claim 1 by:
(a) contacting an optically active N-salicylideneaminoalcohol compound of formula (1):

with a mono-valent or di-valent copper compound, in an inert solvent, wherein R1 represents an alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group, and cycloalkoxy group, an aralkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group,
R2 represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group,

X1 and X2 are the same or different and independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group and two adjacent X1 and X2 together with the benzene ring to which they are bonded may form a l-hydroxy-2- or 2-hydroxy-l-naphthyl group, and the carbon atom denoted by " * " is an asymmetric carbon atom having either an S or R configuration, and with a mono-valent or di-valent copper compound, in an inert solvent, the amount of the mono-valent or di¬valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and (b) reacting a prochiral olefin of formula (3):

wherein R3, R4, R5 and R6 independently represent

a hydrogen atom, a halogen atom,
a (Cl-C10)alkyl group which may be substituted with a halogen atom or a lower alkoxy group,
a (C4-C8)cycloalkyl group,
an aryl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group,
R3 and R4, or R5 and R6 may be bonded at their terminals to form an alkylene group having 2-4 carbon atoms, and
one of R3, R4, R5 and Re groups represents an alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy carbonyl group, of which alkoxy may be substituted with a halogen atom or atoms,
provided that when R3 and R5 are the same, R4 and R6 are not the same, with a diazoacetic acid ester of formula (4):
N2CHCO2R7 (4)
wherein R? is the same as defined above, in the presence of
a chiral copper complex catalyst composition so produced in step (a).

3. A chiral copper complex catalyst composition, substantially as hereinabove described and exemplified.

Documents:

0064-mas-2001 abstract-duplicate.pdf

0064-mas-2001 abstract.pdf

0064-mas-2001 claims-duplicate.pdf

0064-mas-2001 claims.pdf

0064-mas-2001 correspondence-others.pdf

0064-mas-2001 correspondence-po.pdf

0064-mas-2001 description (complete)-duplicate.pdf

0064-mas-2001 description (complete).pdf

0064-mas-2001 form-1.pdf

0064-mas-2001 form-19.pdf

0064-mas-2001 form-26.pdf

0064-mas-2001 form-3.pdf

0064-mas-2001 form-5.pdf

0064-mas-2001 others.pdf

0064-mas-2001 petition.pdf

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Patent Number

217282

Indian Patent Application Number

64/MAS/2001

PG Journal Number

21/2008

Publication Date

23-May-2008

Grant Date

26-Mar-2008

Date of Filing

23-Jan-2001

Name of Patentee

SUMITOMO CHEMICAL COMPANY, LIMITED

Applicant Address

5-33, KITAHAMA 4-CHOME, CHUO-KU, OSAKA 541 - 8550,

Inventors:

#	Inventor's Name	Inventor's Address
1	GOHFU SUZUKAMO	19-10-1008, SHINASHIYAKAMI, SUITA-SHI, OSAKA,
2	MAKOTO ITAGAKI	1-9-1-402, TAMAGAWA, TAKATSUKI-SHI, OSAKA,
3	MICHIO YAMAMOTO	2-12-5, OGINOSATO, OTSU-SHI, SHIGA,

PCT International Classification Number

C07C 69/74

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2000-016279	2000-01-25	Japan
2	2000-018595	2000-01-27	Japan