Iodine/Visible Light Photocatalysis for Activation of Alkynes for Electrophilic Cyclization Reactions

Abstract

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 I2 is applied as both a visible light photocatalyst and a π Lewis acid, enabling the direct activation of alkyne C≡C 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 I2. 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.