二类手性铜催化剂的合成及其在光学活性菊酸合成中的应用研究

Synthesis of Two Types of Chiral Copper Catalysts and Study on Their Application in the Synthesis of Optically Active Chrysanthemic Acid

报道了双口恶唑啉和Ｓｃｈｉｆ碱二类手性配合物的合成及其在光学活性菊酸的不对称合成中的应用。以合成氯霉素中间体的无效体（１Ｓ，２Ｓ）－２－氨基－１－对硝基苯基－１，３－丙二醇为原料，分别制得了二取代双口恶唑啉和Ｓｃｈｉｆ碱二类配体，并将其分别与醋酸铜配合后得到的手性铜催化剂来诱导烯烃（２，５－二甲基－２，４－己二烯和１，１－二苯乙烯）与重氮乙酸酯的不对称环丙烷化反应，最高获得４５．２％ｅ．ｅ．

Two types of chiral copper catalysts were synthesized from the ligands of bisoxazolines(1) and Schiff bases (2) respectively, and their applications were investigated in the asymmetric synthesis of optically active chrysanthemic acid. First, chiral ligands 1 and 2 were prepared from (1S,2S) 2 amino 1 (4 nitrophenyl) 1,3 propanediol, which was an invalid component in the synthesis of chloramphenicol. Then, these two types of ligands were treated with cupric acetate to give chiral copper chelate. These complexes were applied to the reactions of alkyl diazoacetate with the variety of substrates olefins(2,5 dimethyl 2,4 hexadiene and 1,1 diphenylethylene) to give optically active cyclopropanes, and the e.e. values were obtained up to 45.2%.