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In recent years, the activation of unactivated alkyl chlorides through light-induced processes has emerged as a promising field in radical chemistry, and has led to new transformations in organic synthesis. Direct utilization of alkyl chlorides as C(sp3)-hybridized electrophiles enables the facile construction of carbon–carbon and carbon–heteroatom bonds. Furthermore, recent studies in medicinal chemistry indicate that their presence is associated with high levels of success in clinical trials. This review summarizes the recent advances in the photoinduced activation of unactivated alkyl chlorides and discusses the mechanistic aspects underlying these reactions. We anticipate that this review will serve as a valuable resource for researchers in the field of unactivated chemical bond functionalization, and inspire considerable developments in organic chemistry, drug synthesis, materials science and other related disciplines. [ABSTRACT FROM AUTHOR]

Activated alkyl halides have been extensively explored to generate alkyl radicals with Ru- and Ir- photocatalysts for 1,2-difunctionalization of alkenes, but unactivated alkyl bromides remain challenging substrates due to their strong reduction potential. Here we report a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au 3 (tppm) 2 ](OTf) 3 . It can achieve the 1,2-aminoalkylation and 1,2-alkylarylation readily. This protocol has a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96 % yield). It also affords a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C-Br bonds., (© 2023 Wiley-VCH Verlag GmbH.)

A divergent reaction of indoline-derived azadienes with α-bromohydroxamates for the selective synthesis of spiro-indolinepyrrolidinones and indoline-fused diazepinones was disclosed. This reaction sequence involved an initial formation of five-membered spirocyclic products followed by an intramolecular ring-opening and ring expansion to produce seven-membered diazepinones. We demonstrated that controlling the reaction time could modulate the reaction pathway for formation of different molecular frameworks for the same set of substrates. Based on the experimental results, the reaction mechanism was also discussed and proposed to explain the phenomena observed in the process., (© 2023 Wiley-VCH GmbH.)