Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed deca...Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,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 strategy.The protocol has excellent reaction selectivity and functional group compatibility,representing a significant step forward in ketone synthesis.The 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 robustness.Both 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.展开更多
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)+1 种基金Fundamental Research Funds for the Central Universities(0205/14380252),“Innovation&Entrepreneurship Talents Plan”of Jiangsu ProvinceFoundation of Advanced Catalytic Engineering Research Center of the Ministry of Education of Hunan University.
文摘Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,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 strategy.The protocol has excellent reaction selectivity and functional group compatibility,representing a significant step forward in ketone synthesis.The 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 robustness.Both 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.
