The cleavage of carbon–carbon double bonds and their subsequent functionalization is recognized as one of the fundamental reactions in organic chemistry.In contrast to the extensively studied olefin metathesis and ox...The cleavage of carbon–carbon double bonds and their subsequent functionalization is recognized as one of the fundamental reactions in organic chemistry.In contrast to the extensively studied olefin metathesis and oxidative cleavage,we present herein a method that facilitates the deconstructive acylation of aryl alkenes via consecutive photoredox cycles,yielding a range ofα-aryl ketones with moderate to good efficiency.The rational design of tertiary amine as theα-amino radical precursor allows for the efficient cleavage of the carbon–carbon bond.Mechanistic experiments and density functional theory calculations support the formation of a benzylic radical followed by an anion for acylation,enablingσbond cleavage under photoredox conditions.展开更多
基金the National Natural Science Foundation of China(grant no.22271293 the CAS Project for Young Scientists in Basic Research(grant no.YSBR-050)the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB0960301)the Chinese Academy of Sciences for financial support.
文摘The cleavage of carbon–carbon double bonds and their subsequent functionalization is recognized as one of the fundamental reactions in organic chemistry.In contrast to the extensively studied olefin metathesis and oxidative cleavage,we present herein a method that facilitates the deconstructive acylation of aryl alkenes via consecutive photoredox cycles,yielding a range ofα-aryl ketones with moderate to good efficiency.The rational design of tertiary amine as theα-amino radical precursor allows for the efficient cleavage of the carbon–carbon bond.Mechanistic experiments and density functional theory calculations support the formation of a benzylic radical followed by an anion for acylation,enablingσbond cleavage under photoredox conditions.
