Highly Stereoselective Synthesis of 2,2-Disubstituted Vinylphosphonates via Aryl to Vinyl 1,4-Palladium Migration  

作　　者：Yan-Zhen Chen Geng-Yu Bao Xin-Chen Zhan Jian-Guo Fu Xiao-Ming Ji Shu-Sheng Zhang Chen-Guo Feng 

机构地区：[1]The Research Center of Chiral Drugs,Innovation Research Institute of Traditional Chinese Medicine,Shanghai University of Traditional Chinese Medicine,Shanghai,201203 China

出　　处：《Chinese Journal of Chemistry》2022年第18期2188-2192,共5页中国化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(21871284 and 91956113);the fellowship of China Postdoctoral Science Foundation(2021M692152);the Science and Technology Commission of Shanghai Municipality(20XD1423400,21ZR1482100 and 22ZR1458900);the Shanghai Municipal Education Commission(2019-01-07-0010-E00072);the Shanghai Frontiers Science Center for Traditional Chinese Medicine Chemical Biology.

摘　　要：Vinylphosphates play an important role in the fields of synthetic chemistry,pharmaceuticals and material science.It is a long-standing challenge to control the geometry of multi-substituted vinylphosphates.Herein,an efficient method for the synthesis of 2,2-disubstituted vinylphosphonates has been reported.The reaction proceeded via aryl to vinyl 1,4-palladium migration progress,in which two difficulties that the deactivation of palladium catalyst by the coordination of excess secondary phosphine oxide and the competitive cross-coupling to form arylphosphonates are successfully overcome.The judicious selection of phosphine ligand is the key to success.This protocol features excellent regio-and stereoselectivitiy,generally excellent reaction yields and broad substrate socpe.

关 键 词：1 4-Palladium migration Phosphorylation C-H activation STEREOSELECTIVITY CROSS-COUPLING 

分 类 号：O62[理学—有机化学]