A 5πe carbonyl activation mode is reported on the basis of photo-induced single-electron-transfer （SET） oxidation of a secondary enamine. The resultant β-enaminyl radical intermediate was trapped by a wide range o...A 5πe carbonyl activation mode is reported on the basis of photo-induced single-electron-transfer （SET） oxidation of a secondary enamine. The resultant β-enaminyl radical intermediate was trapped by a wide range of Michael acceptors, producing β-alkylation products of β-ketocarbonyls in a highly efficient manner,展开更多
Enantioselective α-photoalkylation of β-ketocarbonyls without any external photosensitizer was described in this work. The photoalkylation reactions, enabled solely by a chiral primary amine catalyst, provided conve...Enantioselective α-photoalkylation of β-ketocarbonyls without any external photosensitizer was described in this work. The photoalkylation reactions, enabled solely by a chiral primary amine catalyst, provided convenient constructions of all-carbon quaternary stereocenters with good activity and high enantioselectivity. Mechanism studies revealed α direct photolytic radical chain process under visible light irradiation.展开更多
基金We thank the National Natural Science Foundation of China （21390400, 21521002, 21572232 and 21672217） and the Chinese Academy of Sciences （QYZDJ-SSW-SLH023） for financial support. S. L. is supported by National Program of Top-notch Young Profes- sionals.
文摘A 5πe carbonyl activation mode is reported on the basis of photo-induced single-electron-transfer （SET） oxidation of a secondary enamine. The resultant β-enaminyl radical intermediate was trapped by a wide range of Michael acceptors, producing β-alkylation products of β-ketocarbonyls in a highly efficient manner,
基金We thank the National Natural Science Foundation of China （Nos. 21390400, 21672217 and 21521002） for financial support. S.L is supported by the National Program of Top-notch Young Professionals and Chinese Academy of Sciences （No. QYZDJSSWSLH023）. We thank Dr. Taishan Wang and Prof. Chunru Wang for their kindly help with EPR simulation.
文摘Enantioselective α-photoalkylation of β-ketocarbonyls without any external photosensitizer was described in this work. The photoalkylation reactions, enabled solely by a chiral primary amine catalyst, provided convenient constructions of all-carbon quaternary stereocenters with good activity and high enantioselectivity. Mechanism studies revealed α direct photolytic radical chain process under visible light irradiation.
