Origins of regio-and stereoselectivity in Cu-catalyzed alkyne difunctionalization with CO_(2) and organoboranes  

作　　者：Lingfei Hu Han Gao Yanlei Hu Xiangying Lv Yan-Bo Wu Gang Lu 

机构地区：[1]School of Chemistry and Chemical Engineering,Key Laboratory of Colloid and Interface Chemistry,Ministry of Education,Shandong University,Jinan,Shandong 250100,China [2]Key Lab for Materials of Energy Conversion and Storage of Shanxi Province and Key Lab of Chemical Biology and Molecular Engineering of Ministry of Education,Institute of Molecular Science,Shanxi University,Taiyuan,Shanxi 030006,China

出　　处：《Organic Chemistry Frontiers》2022年第4期1033-1039,共7页有机化学前沿（英文）

基　　金：We thank the financial support from the Natural Science Foundation of Shandong Province(ZR2019MB049);the National Natural Science Foundation of China(No.21973055);The Taishan Scholar of Shandong Province(No.tsqn201812013);the Qilu Young Scholar of Shandong University are also acknowledged.

摘　　要：The mechanism and origins of regio-and stereoselectivities of Cu-catalyzed alkyne difunctionalization with CO_(2) and trialkyl boranes were computationally investigated.The results show that the vicinal addition to alkyne is disfavored due to the kinetical inertness of the alkyl copper intermediate.The favored geminal addition proceeds through the cationic Cu-mediated stereoselective 1,2-migration pathway.The energy decomposition analysis indicates that theσ)(πPauli repulsion is the dominant factor for controlling the stereoselectivity.

关 键 词：CATALYZED ALKYL ADDITION 

分 类 号：O64[理学—物理化学]