Mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCl_3  

作　　者：XUKailai WUYong XIEDaiqian YANGuosen 

机构地区：[1]DepartmentofChemistry,SichuanUniversity,Chengdu610064,China [2]InstituteofTheoreticalandComputationalChemistry,DepartmentofChemistry,NanjingUniversity,Nanjing210093,China

出　　处：《Chinese Science Bulletin》2004年第9期883-885,共3页

摘　　要：The mechanism of skeletal reorganization of1,6-enynes catalyzed by GaCl3 has been studied with the density functional method at the B3LYP/6-31G* level. Thestructures and energies of the stationary points were calcu-lated to identify the activation barriers. The transition states were testified with vibration analysis and IRC calculations. The results of calculation show that the conversion of 1,6-enynes is a step-wise reaction. The whole reaction process is formation and migration of three-membered cycle involving a three-center and two-electron (3c-2e) bond. High stereose-lectivity of the reaction is in good agreement with experi-mental results.The mechanism of skeletal reorganization of1,6-enynes catalyzed by GaCl3 has been studied with the density functional method at the B3LYP/6-31G* level. Thestructures and energies of the stationary points were calcu-lated to identify the activation barriers. The transition states were testified with vibration analysis and IRC calculations. The results of calculation show that the conversion of 1,6-enynes is a step-wise reaction. The whole reaction process is formation and migration of three-membered cycle involving a three-center and two-electron (3c-2e) bond. High stereose-lectivity of the reaction is in good agreement with experi-mental results.

关 键 词：骨骼重组 氯化镓 金属催化环化 密度功能方法 1 6-enynes 

分 类 号：R687.3[医药卫生—骨科学] R687.3[医药卫生—外科学]