C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the correspo...C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the corresponding polyfluoroarenes and nitriles via C-C(=O)bond cleavage and subsequent decarboxylative arylation process.Various polyfluoroarene and nitrile products are obtained in one pot under cyanide-free conditions.The protocol features high atom economy,broad functional group tolerance and excellent heterocyclic compatibility.The late-stage functionalization of the drug and natural product demonstrated the synthetic utility of our protocol.Furthermore,the decisive role of the dual ligands was clarified and the mechanistic rationale including theβ-C elimination as the rate-limiting step was supported by detailed density functional theory(DFT)studies.展开更多
基金supported by the Shanghai Institute of Materia Medica,the Chinese Academy of ScienceseNational Natural Science Foundation of China(21772211,21920102003)+4 种基金the Institutes for Drug Discovery and Development,Chinese Academy of Sciences(CASIMM0120163006)the Science and Technology Commission of Shanghai Municipality(17JC1405000,18431907100)the Program of Shanghai Academic Research Leader(19XD1424600)the National Science&Technology Major Project“Key New Drug Creation and Manufacturing Program”,China(2018ZX09711002-006)the China Postdoctoral Science Foundation(2019M662854)
文摘C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the corresponding polyfluoroarenes and nitriles via C-C(=O)bond cleavage and subsequent decarboxylative arylation process.Various polyfluoroarene and nitrile products are obtained in one pot under cyanide-free conditions.The protocol features high atom economy,broad functional group tolerance and excellent heterocyclic compatibility.The late-stage functionalization of the drug and natural product demonstrated the synthetic utility of our protocol.Furthermore,the decisive role of the dual ligands was clarified and the mechanistic rationale including theβ-C elimination as the rate-limiting step was supported by detailed density functional theory(DFT)studies.
