Azomethine ylide-formation from N-phthaloylglycine by photoinduced decarboxylation:A theoretical study

作     者：FANG Qiu,DING LiNa & FANG WeiHai* College of Chemistry,Beijing Normal University,Beijing 100875,China 

作者机构：College of Chemistry Beijing Normal University Beijing 100875 China 

出 版 物：《中国科学:化学》 (Scientia Sinica(Chimica))

年 卷 期：2012年第42卷第10期

页      面：1499-1500页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

主　　题：N-phthaloylglycine photodecarboxylation excited state intramolecular proton transfer CASPT2//CASSCF method 

摘      要：In this work,we report the first CASPT2//CASSCF study of the mechanism of the photodecarboxylation of *** charge transfer excited state SCT(1ππ*) is initially populated upon irradiation at 266 *** a result of a fast internal conversion to the lowest excited singlet state SCT-N(1ππ*),this state becomes a favorable precursor state for proton transfer,which triggers ***,the excited state intramolecular proton transfer(ESIPT) and decarboxylation processes proceed in an asynchronous concerted *** ESIPT process is accomplished in the SCT-N(1ππ*) state,but the CO2 molecule is finally formed in the ground state via the SCT/S0 conical *** ylide is formed in the ground state as a complex with CO2.A barrier of ～15 kcal/mol indicates that azomethine ylide is stable in the ground state,which is consistent with the experimental *** work provides mechanistic details about the formation of azomethine ylide by photoreaction of N-phthaloylglycine.