Photocatalytic organic synthesis needs photocatalysts to initiate the reactions and to control the reaction paths. Available photocatalytic systems rely on electron transfer or energy transfer between the photoexcited catalysts and the substrates. We explore a concept based on the photopromoted catalyst coupling to the substrate and the phototriggered catalyst regeneration by elimination from the catalytic cycle. A catalytic amount of elementary I 2 is applied as both a visible light photocatalyst and a π Lewis acid, enabling the direct activation of alkyne CC bonds for electrophilic cyclization reactions, one of the most important reactions of alkynes. Visible light is crucial for both the iodocyclization of the propargyl amide and the deiodination of the intermediate. Singlet oxygen is found to play a key role in the regeneration of I 2 . This system shows good functional group compatibility for the generation of substituted oxazole aldehydes and indole aldehydes. Hence, this study provides a readily accessible alternative catalytic system for the construction of heterocycle aldehyde derivatives by sunlight photocatalysis.
Despite the fact that proton-coupled electron transfer (PCET) has been hypothesized to play a pivotal role in the power conversion efficiency (PCE) of TiO 2 -based solar-energy applications, the specific relationship between the intrinsic nature of visible-light (Vis)-driven PCET reactions and limited PCE gains has not yet been well revealed. Here we studied the detailed kinetics of reactions between various alcohols and radicals ( t Bu 3 ArO • / TEMPO) on a TiO 2 photocatalyst under dye-sensitization Vis irradiation versus direct ultraviolet (UV) irradiation. We found that the rates of Vis-driven reactions were much slower than those of UV-driven reactions under identical light intensity. A similar phenomenon was observed under the off-line dark-reaction conditions in which TiO 2 was prereduced by alcohols. The rapid formation and difficult breakage of the stable "Ti−H" intermediate were proposed to account for the slowed-down PCET effect. This finding revealed an inherent bottleneck in Vis-driven energy conversion applications.
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