手性铜催化剂的制备及在环丙烷羧酸酯不对称合成中的应用

Chiral Copper Complexes for Asymmetric Synthesisof Cyclopropanecarboxylic Esters

３类手性配体ｄ－１０－樟脑磺酸及其衍生物，α－（－）－羟蒎酮及其衍生物，双唑啉衍生物分别与铜（Ⅱ）形成手性铜配合物，催化重氮乙酸酯与１，１－二苯乙烯或异丁烯的环丙烷化加成反应，得到光学活性环丙烷羧酸酯，不对称诱导最高可达９５％ｅ．ｅ．

Three kinds of optically active ligands were combined with copper(Ⅱ)-acetate togive 8 chiral copper complexes:d-camphor-10-sulfonic acid and its derivatives of Schiff base,hydroxypinocamphone and its derivatives of Schiff base,and bis-oxazoline. The opticalyields of 2,2-diphenylcyclopropanecarboxylic ethyl ester were 5%～50e.e..The reactionof diphenylethylene or isobutylene with menthyl diazoaceteta by chiral copper(Ⅱ) bis-oxazo-line gave an enantioselectivity of 81.5%e.e. and 95%e.e.,respectively.