手性螺-环丙烷化合物中手性辅基的区域性转换反应的研究

通过串联的不对称双Michael加成/分子内亲取代反应，一举得到了具有四个新手性中心的螺环/环丙烯类化合物(4).4在丙酮-5%HCl溶液中50℃下发生区域选择性单水解转换反应，得到螺1-溴-4-羟基-5-氧杂-6-氧代双环3.3.0]已-2,3'-(4'-亲核氧基-5'-孟氧基丁内酯)](5),化学产率53%～69%，光学纯度d.e≥98%.4在甲醇/TsOH催化下，实现了区域选择性单醇解转换反应，得到螺1-溴-4-甲氧基-5-氧杂-6-氧代双环3.1.0]已烷-2,3'-(4'-亲核氧基-5'-孟氧基丁内酯)](6),化学产率50%～78%,光学纯度d.e.≥98%.经元素分析，α]D^20,UV,IR,1^HNMR,13^CNMR,MS以及X射线四圆衍射测定，确认了它们的化学结构。

Studyes on regioselective transformation of auxiliary group in chiral spiro-cyclopropane derivatives

The functionalized spiro-cyclopropane derivatives 4 containing four stereogenic centers were obtained in good yields with d.e≥98% via tandem double Michael addition/internal nucleophilic substitution of the onvel chiral synthon 1. 4-was undergone regioselective transformation of the auxiliary goup under presence of acetone/5% HCl to afford single hydrolytic products 5 in yields of 50%～78% with d.e. .≥98% and also to afford single alcoholic products 6 in yields of 50% ～78% with d.e.≥98% under presence of CH3OH/p-TsOH. The novel chiral compounds 5a～5f and 6a～6e were identified on the basis of their analytical data and spectroscopic data, such as UV, IR, 1^H NMR, 13^C NMR, MS elementary analysis and X-ray crystallography.