The Effect of HSAB on Stereoselectivity: Copper and Gold Catalyzed 1,3-Phosphatyloxy and 1,3-Halogen Migration Relay to 1,3-Dienes
作者单位：School of Chemistry and Chemical EngineeringSun Yat-sen 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：The origin of stereodivergence between copper and gold catalyzed cascade 1,3-phosphatyloxy and 1,3-halogen migration fromα-halo-propargylic phosphates to 1,3-Dienes is rationalized with density functional theory（DFT）*** studies reveal the significant role of the relative hardness/softness of the metal centers in determining the reaction mechanism and the stereo *** relative harder Cu（I/Ⅲ）center prefers an associated pathway with the aid of phosphate group,leading to the（Z）-1,*** contrast,the relative softer Au（I/Ⅲ）center tend to undergo a dissociative pathway without coordination to phosphate group,resulting in the（E）-1,*** addition is suggested to be the rate-determining step for gold catalysis,where the E-type of transition state is favored due to steric *** findings indicate the intriguing role of hard-soft/acid-bases（HSAB）theory in tuning metal catalyzed transformations with functionalized substrates.