手性环丙烷二羧酸的合成

Syntheses of Chiral Cyclopropanedicaboxylic Acids

具有光学活性的环丙烷衍生物可以由烯烃与手性卡宾或类卡宾试剂反应制得。应用手性钴或铜络合物催化剂于富电子烯烃与重氮化合物反应。

(1R,2R) trans-1,2-cyglopropanedicarboxylic acid (3) and (1R,2R) trans-3,3-dimethyl-1,2-cyclopropanedicacid (5) were prepared by reaction of (-) dim-enthyl fumarate with gem-dihalides (CH_2Br_2, CH_3CCl_2CH_3) catalyzedbby cobalt (0), nickel(0) complex and Zn under ultrasonic waves. The chemical and optical yield of 3 increasedto 79.5% and 78% respectively. The chemical and opticl yield of 5 increased to 55.3%and 47.8% respectively. Addition of bidentate ligands was useful for CH_2CBr_2 system, butnot for CH_3CCl_2CH_3 system. Two optical isomers of cyclopropane derivatives were seperatedfrom HPLC by chiral column PTrMA.