A theoretical study on the alkene insertion step in Rh-Yanphos catalyzed hydroformylation  

作　　者：Xiao-Jie Du Yan-Hui Tang Xin Zhang Ming Lei 

机构地区：[1]State Key Laboratory of Chemical Resource Engineering,Institute of Materia Medica,College of Science,Beijing University of Chemical Technology [2]College of Material Science and Engineering,Beijing Institute of Fashion Technology

出　　处：《Chinese Chemical Letters》2013年第12期1083-1086,共4页中国化学快报（英文版）

基　　金：in part supported by the National Natural Science Foundation of China (Nos. 21072018 and 21203006)

摘　　要：This paper studied the mechanism of the alkene insertion elementary step in the asymmetric hydroformylation （AHF） catalyzed by RhH（CO）2[（R,S）-Yanphos] using four alkene substrates （CH2=CH- Ph, CH2=CH-Ph-（p）-Me, CH2=CH-C（==O）OCH3 and CH2=CH-OC（=O）-Ph, abbreviated as A1-A4）. Interestingly, the equatorial vertical coordination mode （A mode） with respect to the Rh center was found for AI and A2 but not for A3 and A4, although the equatorial in-plane coordination mode （E mode） was found for A1 -A4. The relative energy of the E mode of the -q2-intermediates is lower than that of the A mode. In the alkene insertion step, Path 1 is more favorable than Path 2 for this system. As for AI and A2, there could be a transformation between 2eq and 2ax.This paper studied the mechanism of the alkene insertion elementary step in the asymmetric hydroformylation （AHF） catalyzed by RhH（CO）2[（R,S）-Yanphos] using four alkene substrates （CH2=CH- Ph, CH2=CH-Ph-（p）-Me, CH2=CH-C（==O）OCH3 and CH2=CH-OC（=O）-Ph, abbreviated as A1-A4）. Interestingly, the equatorial vertical coordination mode （A mode） with respect to the Rh center was found for AI and A2 but not for A3 and A4, although the equatorial in-plane coordination mode （E mode） was found for A1 -A4. The relative energy of the E mode of the -q2-intermediates is lower than that of the A mode. In the alkene insertion step, Path 1 is more favorable than Path 2 for this system. As for AI and A2, there could be a transformation between 2eq and 2ax.

关 键 词：DFT Hydroformylation Mechanism Alkene insertion Coordination mode 

分 类 号：O643.32[理学—物理化学]