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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 [Au3(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. [ABSTRACT FROM AUTHOR]

Alkenes, Difunctionalization, Gold Catalysis, Photoredox Catalysis, Radical In their Research Article (e202305121), Jin Xie and co-workers overcome the inherent redox potential limit of alkyl bromides and achieve 1,2-aminoalkylation and 1,2-alkylarylation of different alkenes by using the inner single electron transfer mechanism of an excited trinuclear gold catalyst. Keywords: Alkenes; Difunctionalization; Gold Catalysis; Photoredox Catalysis; Radical EN Alkenes Difunctionalization Gold Catalysis Photoredox Catalysis Radical 1 1 1 08/17/23 20230821 NES 230821 B Inert alkyl bromides b are rarely used in photoinduced 1,2-difunctionalization of alkenes due to their strong reduction potential and bond dissociation energy. [Extracted from the article]