手性铜络合物催化2,5-二甲基-2,4-己二烯不对称环丙烷化反应的研究(Ⅰ)

Study on Asymmetric Cyclopropanation of 2,5 Dimethyl 2,4 hexadiene Catalyzed by Chiral Copper(Ⅱ) Complexes

手性铜络合物催化２，５－二甲基－２，４－己二烯不对称环丙烷化反应的研究（Ⅰ）陈惠麟王胜国郑卓（中国科学院大连化学物理研究所大连１１６０２３）关键词手性铜（Ⅱ）络合物环丙烷化不对称反应分类号Ｏ６４３．３２第一菊酸乙酯［２，２－二甲基－３－（２－甲基丙烯...

The catalytic asymmetric reactions of diazoacetate esters with olefins are useful method for generating enantiomers of cyclopropane carboxylates, which are intermediates in the synthesis of pyrethroid insecticides. In this word the cyclopropanation catalyzed by seven chiral copper(Ⅱ). Schiff base complexes derived from ( R ) 1 ( p nitrophenyl) 2 amino propylene 1,3 glycol, ( R,R and ( S,S ) 1,2 diamino cyclohexane was studied. The e.e. values of R trans isomer in the reaction of 2,5 dimethyl 2,4 hexadiene DMHDE with N 2CHCOOMe n L catalyzed by complexes Ⅳ and Ⅶ reach 84.3% and 85.5%, respectively. It is for the first time to find an abnormal cis/trans ratio of 83/17 in the reaction catalyzed by complex Ⅵ with N 2CHCOO( n Bu) as diazo compound.