Effects of (BCO)_n Substituent on Claisen Rearrangement of Phenyl Allyl Ether

作     者：PEI Xiao-qin JIAN Jian-feng WU Hai-shun 

作者机构：Department of Chemistry Shanxi Normal University Linfen 041004 P. R. China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2007年第23卷第2期

页      面：212-216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] 

基　　金：the National Natural Science Foundation of China(No 20471034) Youth Foundation of Shanxi Province,China(No 20051011) 

主　　题：Transition states Structures Energetics 

摘      要：Considering the isolobal analogy between two fragments CH and BCO, the calculations on the reactants, products, and transition states for the Claisen rearrangement of （BCO）n-substituted phenyl allyl ethers at the B3P86/ 6-311 ＋ G^＊＊ level was performed in this study. The transition states of （BCO）n-substituted systems have looser and more structures with dipole nature. The substitutions of CH by BCO do favor the reduction of the free energies of activation and the enhancement of stabilization of both reactants and products. A Marcus theory and frontier molecular orbitals were used to separate the thermodynamic and intrinsic contributions to the activation energies.