Palladium Difluorocarbene Involved Catalytic Coupling with Terminal Alkynes

作     者：Xue-Ying Zhang Xia-Ping Fu Shu Zhang Xingang Zhang 

作者机构：Key Laboratory of Organofluorine ChemistryCenter for Excellence in Molecular SynthesisShanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesChinese Academy of SciencesShanghai 200032(China) College of ChemistryHenan Institute of Advanced TechnologyZhengzhou UniversityZhengzhou 450001(China) School of Materials and EnergyUniversity of Electronic Science and Technology of ChinaChengduSichuan 611731(China) 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2020年第2卷第5期

页      面：293-304页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(nos.21931013,21991122,21672238,and 21421002) the Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000) 

主　　题：Alkynes cross-coupling difluorocarbene difluoromethyl palladium 

摘      要：Difluoromethylated alkynes are a versatile synthon for the diversity-oriented synthesis of difluoromethyl compounds that are of great interest in life and materials ***,the catalytic cross-coupling for the synthesis of difluoromethylated alkynes remains challenging,despite impressive achievements made in the cross-coupling reactions for alkynes,including the Sonogashira ***,we report a palladium difluorocarbene involvement in catalytic coupling with terminal alkynes,representing a new mode of conjugation reaction,which circumvents the radical pathway usually encountered during the coupling of alkynes with fluoroalkyl *** reaction uses inexpensive and abundant industrial raw material chlorodifluoromethane(ClCF_(2)H)as the difluorocarbene precursor,and features cost-effectiveness,excellent functional group tolerance,and broad substrate scope,including synthesis of drug-like complex *** mechanistic studies showed a unique catalytic pathway of this process,in which additive hydroquinone plays a pivotal role in promoting the reaction.