Search

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]

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. [ABSTRACT FROM AUTHOR]

Keywords: Alkenes; Difunctionalization; Gold Catalysis; Photoredox Catalysis; Radical EN Alkenes Difunctionalization Gold Catalysis Photoredox Catalysis Radical 1 1 1 08/21/23 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. 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. Inside Back Cover: Trinuclear Gold-Catalyzed 1,2-Difunctionalization of Alkenes (Angew. [Extracted from the article]

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]