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Directed ortho-C(sp2)─H Functionalization of N/O-Containing Heterocycles: Catalytic and Mechanistic Insights
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DOI：10.1002/ajoc.70462.png)
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Abstract
En 中文
C─H activation has revolutionized synthetic organic chemistry by enabling site-selective functionalization of unactivated C─H bonds, offering superior atom and step economy compared to conventional existing methodologies. This review highlights the recent advances in directing group (DG)-assisted, transition metal-catalyzed ortho-C(sp2)–H functionalization of pharmacologically relevant N/O-containing heterocycles that include benzoxazinones, quinoxalin-2(1H)-ones, and 2-arylquinazolin-4(3H)-ones. The key transformations include Pd-/Ru-/Rh-catalyzed ortho-acyloxylation, halogenation, amidation, alkenylation, alkylation, and annulation using diverse coupling partners such as sulfonyl azides, N-halosuccinimides (NXS), dioxo acids, alkenes, and azo-compounds. Emerging sustainable approaches, including microwave-assisted synthesis, electrochemical C─H activation, heterogeneous catalysis, and photoredox-mediated transformations, are also discussed. Mechanistic insights reveal common pathways involving cyclometallation, oxidative addition/reductive elimination (Pd(II)/Pd(IV), Rh(III)), and migratory insertion, with DGs playing a crucial role in the regioselectivity. Overall, this review provides a comprehensive overview of recent progress in transition metal-catalyzed C─H functionalization in a regioselective manner, emphasizing synthetic utility, mechanistic understanding, and applications in drug discovery and advanced organic synthesis.
Keywords:
C─H activation
N-directed
N-heterocycles
regioselectivity
transition metals
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