Angewandte Chemie · 2018 · 31 citations · 53 references
Natural SciencesChemistryMedicinal ChemistryBiocatalysisCatalysisSynthetic Medicinal ChemistryHeterocycle SynthesisMacrocycle SynthesisOrganic SynthesisPhotocatalysisPhotochemical SynthesisPhotochemistryFunctional Group ToleranceKetonesLactam MacrocyclesLactam SynthesisMild Reaction ConditionsPhotocatalytic SynthesisSubstrate ScopeSubstrate Scope Expansion
Abstract Reported is a novel two‐step ring‐expansion strategy for expeditious synthesis of all ring sizes of synthetically challenging (hetero)aryl‐fused medium‐sized lactams from readily available 5–8‐membered cyclic ketones. This step‐economic approach features a remote radical (hetero)aryl migration from C to N under visible‐light conditions. Broad substrate scope, good functional‐group tolerance, high efficiency, and mild reaction conditions make this procedure very attractive. In addition, this method also provides expedient access to 13–15‐membered macrolactams upon an additional one‐step manipulation. Mechanistic studies indicate that the reaction involves an amidyl radical and is promoted by acid.
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Catalytic alkylation of remote C–H bonds enabled by proton-coupled electron transfer
Gilbert J. Choi, Qilei Zhu, David C. Miller et al. · Nature · 2016 · 770 citations · Full text