非对称氮杂环丙烷的亲核开环反应及其区域选择性_马琳鸽.pdf

16 2 化　学　进　展 Vol.16 No.2 2004 3 PROGRESS IN CHEMISTRY 　Mar., 2004 非对称氮杂环丙烷的亲核开环反应及其区域选择性＊ 马琳鸽　许家喜＊＊ (北京大学化学与分子工程学院化学生物学系教育部生物有机与分子工程重点实验室　北京100871) 　　本 系统地总结了各类亲核试剂对非对称氮杂环丙烷(吖丙啶)的亲核开环反应及开环的区域 选择性。氮杂环丙烷亲核开环的区域选择性是一种空间效应和电子效应平衡的结果, 非芳基和非烯基取代 的氮杂环丙烷的亲核开环通常发生在氮杂环丙烷取代少的碳原子上, 空间效应起主导作用;而芳基和烯基取 代的氮杂环丙烷的亲核开环通常发生在氮杂环丙烷芳甲位和烯丙位的碳原子上, 电子效应起主导作用, 烯基 取代的氮杂环丙烷的亲核开环还可以发生在烯基的β-碳原子上;分子内的亲核开环反应主要受成环时环大 小的控制, 成环时的倾向是五元环六元环七元环。 对于亲核试剂, 一般的亲核试剂也同时受电子效应和 空间效应的影响;而亲核性强的亲核试剂通常只受空间效应的影响。容易生成稳定自由基的亲核试剂容易 发生单电子转移机理的开环反应, 生成相当于亲核试剂进攻氮杂环丙烷中取代多的碳原子得到的开环产物。 　氮杂环丙烷　吖丙啶　亲核试剂　亲核开环　区域选择性 :O621.3;O623.7　:A 　:1005-281X (2004)02-0220-16 Nucleophilic Ring Opening Reaction of Unsymmetric Aziridines and Its Regioselectivity ＊＊ Ma Linge 　Xu J iaxi (Key La oratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China) Abstract 　Nucleophilic ring opening reaction of unsymmetric aziridines and its regioselectivity with various nucleo- phileswas reviewed systematically.The regioselectivity is controlled y a alance etween steric hindrance and electronic effect in an aziridine ring.Nucleophilic ring opening reaction of non-aryl and non-alkenyl su stituted aziridines occurs generally on the less su stituted car on atom in their aziridine rings, controlled y steric hindrance.However, the reac- tion of aryl and alkenyl su stituted aziridines does on arylmethyl and allyl car on atom, controlled y electronic effect, and the reaction of alkenyl su stituted aziridines can also occur on the β-car on atom of the alkenyl gro