【摘 要】
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The origin of stereodivergence between copper and gold catalyzed cascade 1,3-phosphatyloxy and 1,3-halogen migration from α-halo-propargylic phosphates to
【机 构】
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School of Chemistry and Chemical Engineering,Sun Yat-sen University,Guangzhou 510275
论文部分内容阅读
The origin of stereodivergence between copper and gold catalyzed cascade 1,3-phosphatyloxy and 1,3-halogen migration from α-halo-propargylic phosphates to 1,3-Dienes is rationalized with density functional theory(DFT)studies.Our studies reveal the significant role of the relative hardness/softness of the metal centers in determining the reaction mechanism and the stereo selectivity.The relative harder Cu(I/III)center prefers an associated pathway with the aid of phosphate group,leading to the(Z)-1,3-dienes.In contrast,the relative softer Au(I/III)center tend to undergo a dissociative pathway without coordination to phosphate group,resulting in the(E)-1,3-dienes.Oxidative addition is suggested to be the rate-determining step for gold catalysis,where the E-type of transition state is favored due to steric effect.Our findings indicate the intriguing role of hard-soft/acid-bases(HSAB)theory in tuning metal catalyzed transformations with functionalized substrates.
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