Stereochemistry of the coupling step in photo-S_(RN) 1 reaction

作     者：WU, Bi-Qi ZENG, Fan-Wen ZHAO, Yong WU, Guo-Sheng Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 

作者机构：Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：1992年第10卷第3期

页      面：253-261页

核心收录：

学科分类：07[理学] 0703[理学-化学] 

基　　金：Project supported by the National Natural Science Foundation of China 

主　　题：Ph Stereochemistry of the coupling step in photo-S reaction RN 

摘      要：The photo-S_(RN) 1 reaction of (+)-camphor and aryl halides was investigated in order to estimate the stereochemistry of the coupling step of aryl radicals with a nucleophile. The ratio of endo to exo products determined by ~1H NMR and CD spectra was found to be 99:1. MNDO calculations of the orbital parameters showed a favorable one-sided overlap of the enolate ion with the SOMO of aryl radical. In addition, fragmentation of (ArX)^- was found to be related to the energy of SOMO of (ArX)^-.