Process for preparing halogenated cyclopropane derivatives

A process for preferentially preparing an optically active compound represented by the following general formula (I):

• wherein:
• the stereochemical configuration at 1-position is S-configuration;
• X represents chlorine atom, bromine atom, or iodine atom;
• R represents a C1-10 alkyloxy group which may have one or more halogen atoms or C1-10 alkyloxy groups;
• an aralkyloxy group constituted by an aryl group which may have a substituent(s) and a C1-10 alkyloxy group;
• an aryloxy group having one or more aryl groups which may be substituted;
• a C1-10 alkylthio group which may have one or more halogen atoms;
• an aralkylthio group constituted by an aryl group which may have a substituent(s) and a C1-10 alkylthio group;
• amino group;
• or
• a substituted amino group which has one or more substituents selected from the group consisting of a C1-10 alkyl group, an aryl group which may be substituted, an aralkyl group constituted by an aryl group which have a substituent(s) and a C1-10 alkyl group, and an acyl group;
• provided that substituents of the substituted aryl groups are selected from the group consisting of a halogen atom, a C1-10 alkyl group, a C1-10 halogenoalkyl group, a C1-10 alkyloxy group, a carbamoyl group which may be substituted, hydroxyl group, nitro group, cyano group, and an amino group which may be substituted;
• which process comprises reacting a compound represented by the formula:
• N2CHCOR wherein R is the same as that defined above with a compound represented by the formula:
• CH2═CXF wherein X is the same as that defined above in the presence of a catalyst obtainable from a copper source, and at least one chiral ligand selected from the group consisting of an oxazoline-type ligand of the formula:
• wherein R1 represents a lower alkyl group having 1 to 5 carbon atoms or phenyl group which may be substituted, and the stereochemistry of each asymmetric carbon bound by R1 is S-configuration and R2 represents hydrogen atom or methyl group, and
• a diamine-type ligand of the formula:
• wherein R3 represents benzyl group, 2,4,6-trimethyiphenylmethyl group, or diphenylmethyl group, and the stereochemistry of each asymmetric carbon atom bound by the phenyl group is R-configuration.