Mechanism on Remarkably Stereospecific Monochlorination of Adamantylideneadamantane
作者单位：Key Laboratory for Green Chemical and TechnologySchool of Chemical Engineering and TechnologyTianjin 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] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
摘 要：Herein,we report a comprehensive theoretical investigation on highly stereospecific monochlorination of adamantylideneadamantane（Ad=Ad）with Cl2 and NCS in *** the reaction without radical initiators,ion-pair mechanism well rationalizes the unique *** involves three consecutive steps:formation of ion-pair species（Ad=Ad-Cl+/Cl-and Ad=Ad-Cl+/NS-）,stereospecific proton abstraction from 4-axial（4-a）position and kinetically preferred intramolecular 4-equatorial（4-e）cyclopropylcarbinyl-homoallylic *** to the reaction with the presence of radical initiators,the free radical mechanism fails to explain the experimental results,but the radical cation mechanism works *** this channel,Ad=Ad+· is formed via one-electron oxidization with the assistance of oxidants like Cl·,NS·and Ad=Ad-Cl+.Then the stereospecific 4-e-Ad=Ad+formed by hydrogen loss from 4-e position of Ad=Ad+·interacts with chloride anion and gives the final product.