Theoretical Study on Cyclopropanation of endo-Dicyclopentadiene with Zinc Carbenoids
作者单位：Key Laboratory for Green Chemical and TechnologySchool of Chemical Engineering and TechnologyTianjin University Department of ChemistrySchool of ScienceTianjin University
会议名称：《中国化学会第十二届全国量子化学会议》
会议日期：2014年
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]
摘 要：A computational study using M06 method on the cyclopropanation of endo-dicyclopentadiene with Simmons-Smith zinc carbenoids is *** channel proceeds via the methylene-transfer *** channels with IZn CH2I attacking the double bonds from the exo-face have much lower barrier（about 16.17-18.43 kcal/mol）in gas phase,compared with the channels from the endo-face（21.80-31.13 kcal/mol）.So P1 and P3 are the primary cyclopropanated compounds,and P5 is the sole final product,representing remarkable *** the bulk solvent effect of diethyl ether,the barriers are decreased about 0.50-7.77 kcal/*** solvated（ICH2）2Zn can further reduce the barriers about 0.18-2.30 kcal/mol and retain the *** computational results suggest that both IZn CH2I and（ICH2）2Zn might be the active species in real reaction system,in good agreement with experimental *** regard to the solvent effect,the polar continuum model is more realistic than the direct involvment of diethyl ether molecules.