Radical addition is a robust tool for bond formation. While ketyl radical reactivity of aldehydes by photoredox has been wellestablished, herein, we have now revealed a pathway for umpolung addition of aldehydes with or without external reductant. Hence, the reductive alkylations and challenging benzylations of nitrogen heteroarenes (i.e., Minisci reactions) are enabled by the bromidepromoted visible light-mediated photocatalysis. The present protocol offers a mild, viable method for late-stage alkylations and transitionmetal-free benzylations of biologically active nitrogen-heteroarene molecules. Mechanistic studies are indicative of a bromide-initiated acyl radical mechanism in the absence of external reductant.

Photocatalytic aerobic decarbonylative C–C coupling/alkylations of N-heteroarenes with aldehydes have been disclosed for the first time.

A visible-light-mediated photoredox Minisci-type alkylation with ethers as the alkylating reagent is reported. User-friendly LiBr has been found to be the key promoter for this radical coupling. The reaction exhibits broad functional group tolerance for both C2 and C4 couplings/ alkylations of quinolines. Mechanistic studies suggest that the bromide additive could not only dramatically enhance the reaction but also alter the reaction mechanism probably over a reductive catalytic cycle.

Ao ne-pot synthesis of 4-quinolones starting from indoles is disclosed. This cascade reactioni nvolves a photocatalytic aerobico xidation of indoles using visible light and as ubsequent base-promoted Camps cyclization. The advantages of the present protocol include the use of environmentally benign and inexpensive oxygen as the sole oxidant,e asy handling at room temperature, as well as step-and atom-economy.Scheme1.Formation of 4-quinolones from 2-aminophenones.[a] Dr.

Organophosphorus compounds (OPCs) have wide application in organic synthesis, material sciences, and drug discovery. Generally, the vast majority of phosphorus atoms in OPCs are derived from white phosphorus (P 4 ). However, the large-scale preparation of OPCs mainly proceeds through the multistep and environmentally toxic chlorine route from P 4 . Herein, we report the direct benzylation of P 4 promoted by visible light. The cheap and readily available benzyl bromide was used as a benzylation reagent, and tetrabenzylphosphonium bromide was directly synthesized from P 4 . In addition, the metallaphotoredox catalysis strategy was applied to functionalize P 4 for the first time, which significantly improved the application range of the substituted benzyl bromide.