Decarboxylative Acylation of Carboxylic Acids:Reaction Investigation and Mechanistic Study
作者机构:State Key Laboratory of Coordination ChemistryJiangsu Key Laboratory of Advanced Organic MaterialsChemistry and Biomedicine Innovation Center(ChemBIC)School of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210023 State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryShanghai 200032 Advanced Catalytic Engineering Research Center of the Ministry of EducationHunan UniversityChangsha 410082
出 版 物:《CCS Chemistry》 (中国化学会会刊(英文))
年 卷 期:2022年第4卷第7期
页 面:2469-2480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:the financial support from the National Natural Science Foundation of China(grant nos.22001117,21971108,21971111,and 21732003) the Natural Science Foundation of Jiangsu Province(grant no.BK20190006) Fundamental Research Funds for the Central Universities(0205/14380252),“Innovation&Entrepreneurship Talents Plan”of Jiangsu Province Foundation of Advanced Catalytic Engineering Research Center of the Ministry of Education of Hunan University
主 题:metallaphotoredox decarboxylative acylation ketones synthesis dual-catalysis carboxylic acid
摘 要:Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group ***,we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters.A wide range of structurally diverse asymmetrical aryl alkyl and dialkyl ketones have been constructed in yields of up to 98% with this *** protocol has excellent reaction selectivity and functional group compatibility,representing a significant step forward in ketone *** one-pot decarboxylative acylation at the gram scale from two different carboxylic acids and the late-stage application for the synthesis of complex ketones shows its synthetic *** mechanistic experiments and density functional theory(DFT)calculations suggest that the decarboxylative acylation reaction operates via an underdeveloped Ni(Ⅰ)-Ni(Ⅱ)-Ni(Ⅰ)-Ni(Ⅲ)-Ni(Ⅰ)catalytic cycle.