The role of Cul in the siloxane-mediated Pd-catalyzed cross-coupling reactions of aryl iodides with aryl lithium reagents  

作　　者：Yu Chen Xiao Zhang Fang Liu Gucheng He Ju Zhang K.N.Houk Amos BSmith III Yong Liang 

机构地区：[1]State Key Laboratory of Coordination Chemistry,Jiangsu Key Laboratory of Advanced Organic Materials,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China [2]Department of Chemistry,University of Pennsylvania,PA 19104,United States [3]Department of Chemistry and Biochemistry,University of California,CA 90095,United States

出　　处：《Chinese Chemical Letters》2021年第1期441-444,共4页中国化学快报（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(No.21803030);the Fundamental Research Funds for the Central Universities,the National Thousand Young Talents Program;the Jiangsu Innovation&Entrepreneurship Talents Plan;the NSF of Jiangsu Province(No.BK20170631)in China;the National Institutes of Health(No.CA-019033);the National Science Foundation in USA(No.CHE-1361104)。

摘　　要：Experiments indicate that a catalytic amount of Cul plays an important role in the siloxane-mediated Pd-catalyzed cross-coupling reactions with the direct use of organolithium reagents.Addition of organolithium to the siloxane transfer agent generates an organosilicon intermediate.DFT calculations indicate that Cul initially accelerates the Si-Pd(Ⅱ) transmetalation of the organosilicon intermediate by the formation of CuI_(2)^(-).Subsequently,CuI_(2)^(-)works as a shuttle between the Si-Cu(Ⅰ) and Cu(Ⅰ)-Pd(Ⅱ)transmetalation processes.

关 键 词：CROSS-COUPLING CUI DFT calculation Reaction mechanism TRANSMETALATION 

分 类 号：O621.251[理学—有机化学]