Photoinduced External Oxidant-free Oxidative Reactions With H₂ Evolution

Outstanding one of the natural science,Chemistry has adventurously improved both the development of material and spiritual civilization,especially the organic chemistry.Based on its unique properties,radical chemistry serves dramatically in chemical bonds construction,which leads numerous scientists flood into C-H activation.Oxidative coupling promotes the radical C-H activation blooming after multiple-dimension revolution.Through accumulation of experience and practice to explore,Modern sciences are highly differentiation and integration.Interdisciplines inevitably meet the trend of“science bond”regeneration.So comes to the photoredox and proton reduction dual catalytic system without external oxidant.1.Herein,we unprecedentedly present a bioorthogonal strategy combining cysteine contained polypeptide or protein with functional indene as linker under external oxidant free condition with hydrogen evolution.Different from the traditional Thiol-Ene mechanism and hydrofunctional adduct,we prefer the double-bond remained transformation originated from the alkene radical cation formed through the phororedox and proton reduction catalytic cycle.2.A visible-light-promoted Lewis-pair induced S-H homolysis for the construction of Thiol-Ene Coupling labeled deuterotrifluoromethyl compounds is investigated, where D₂O may act as both a Lewis acid and radical quencher.3.we line out an intramolecular ene-acid six-member annulation by the synergistic effect of the visible-light promoted photoredox and proton reduction dual catalytic system under external oxidant free condition with hydrogen evolution;4.Using tetrahydronaphthalene as the sole substrate,whose benzylic C_sp3-H bond can be directly oxidized to its carbon radical cation through a visible-light induced photocatalysis and proton reduction catalysis pathway,a cooperative catalytic sacrificial acceptorless aromatization of cyclohexenes is achieved together with double hydrogen evolution;5.Similar to the direct oxidation of benzylic C_sp3-H bond surrendered to the visible light induced oxidant free cross coupling hydrogen evolution methodology,we extend a conceptually novel catalytic dehydrogenative acceptorless cascade organic synthesis between indane and alcohols,which may be owe to the radical cation.