无配体条件钯催化内炔的氢膦酰化反应合成(E)-烯烃膦酸酯类化合物  

Ligand-Free Pd-Catalyzed Hydrophosphorylation of Internal Alkynes for the Synthesis of E-Vinylphosphonates

作　　者：许振丽 张宗雪 孟晨湘 张萧雅 许凯[2] 刘澜涛[2,3] 王涛[2] 徐海云[2] 毛国梁[1] Xu Zhenli;Zhang Zongxue;Meng Chenxiang;Zhang Xiaoya;Xu Kai;Liu Lantao;Wang Tao;Xu Haiyun;Mao Guoliang(College of Chemistryand Chemical Engineerings Northeast Petroleum University,Daqing,Heilongjiang 163318;Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals,College of Chemistry and Chemical Engineerings Shangqin Normal University,Shangqiu,Henan 476000;College of Chemistry and Molecular Engineering,Zhengzhou University,Zhengzhou 450001)

机构地区：[1]东北石油大学化学化工学院,黑龙江大庆163318 [2]商丘师范学院化学化工学院药物绿色合成河南省工程实验室,河南商丘476000 [3]郑州大学化学与分子工程学院,郑州450001

出　　处：《有机化学》2021年第8期3264-3271,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21572126,21202095);河南省技术人员队伍建设(No.C20150030);河南省科技创新人才计划(No.184100510011);河南省自然科学基金(No.212300410379);河南省科技重大专项(No.192102110222)资助项目.

摘　　要：报道了在不同醇中无配体条件下钯催化二苯基 H-亚膦酸酯对内炔的氢膦酰化反应合成E-烯烃膦酸酯类化合物的方法.这种实用且通用的三组分反应涉及二苯基 H-亚膦酸酯对相对惰性内炔的顺式加成,以及伴随的二苯基 H-亚膦酸酯的酯交换过程.反应具有高立体选择性、宽泛的底物范围和无需额外配体等显著特点.A ligand-free Pd-catalyzed hydrophosphorylation of internal alkynes with diphenyl H-phosphonate in various alcohols for the synthesis of E-vinylphosphonates has been reported.This pratical and versatile three-component reaction involves the syn-addition of diphenyl H-phosphonate towards relatively inactive internal alkynes,as well as the concomitant transesterification of diphenyl H-phosphonate.The remarkable features include high stereoselectivity,wide substrate scope and the absence of additional ligands.

关 键 词：加成反应 三组分反应 乙烯基膦酸酯 钯 内炔 

分 类 号：TQ225.24[化学工程—有机化工]