Paternò-Büchi反应区域选择性.pdfVIP

第 19 卷 第 6 期 化　学　进　展 Vol. 19 No. 6 2007 年 6 月 PROGRESS IN CHEMISTRY 　June , 2007 PaternòBüchi 反应的区域选择性 孔峰峰　宋钦华 ( 中国科学技术大学化学系 　合肥 230026) 摘 　要 　PaternòBüchi (PB) 反应 ,即羰基烯的[2 + 2 ]光环化加成反应 ,利用其特殊的区域及立体选择性 可以合成一些结构精巧的取代氧杂环丁烷。随着 PB 反应在有机合成中越来越广泛的应用 ,人们对 PB 反 应的区域选择性的研究也越来越深入。在 PB 反应发现之初 ,人们一直用“最稳定的双自由基规则”解释其 区域选择性 ,这一规则对有些体系却不适用 ,近年来有人开始运用“自旋化学”理论来解释区域选择性。本论 文结合作者的研究工作 ,评述了近年来 PB 反应的区域选择性的研究进展 ,重点阐述了反应温度、反应物的 取代基对 PB 反应区域选择性的影响及其规律。 关键词 　PaternòBüchi (PB) 反应 　区域选择性 　最稳定的双自由基规则 　自旋化学 　SalemRowland 规 则 　温度效应 　取代基效应 + ( ) 中图分类号: O62116 ; O6213 7 　文献标识码 : A 　文章编号 : 1005281X 2007 Regioselectivity in the PaternòBüchi Reaction Kong Fengfeng 　Song Qinhua (Department of Chemistry , University of Science and Technology of China , Hefei 230026 , China) Abstract 　The PaternòBüchi ( PB ) reaction , which is a photochemical [ 2 + 2 ] cycloaddition of carbonyl compounds with alkenes , is used to construct some substituted oxetanes by taking advantage of its special stereo and regioselectivity. With the more and more applications in organic synthesis of the PB reaction , its regioselectivity has attracted more and more attention. The most stable biradical rule , which was put forward at the beginning of the discovery of the PB reaction , was used to explain its regioselectivity. However , it was not applicable for some systems. People began to apply spin chemistry to explain the regioselectivity recently. We have summarized the recent progress in studies