Tunable Dearomative Intermolecular Hydrofunctionalization of Heteroarenes via Acridine/Acridinium Photoredox Catalysis
Year: 2026
Type: preprint
Abstract: Development of mechanistically divergent steps in photocatalytic manifolds by distinct modes remains understudied, impeding their implementation in synthetic methodology. In this study, we present a tunable dearomative hydroetherification, hydroesterification, and hydroamination of heteroarenes via two distinct mechanistic pathways for the synthesis of C-2 regioselective C(sp3) enriched 3D complex dihydrobenzofurans and indolines under photoredox conditions from readily available feedstock. The reaction operates via two independent two mechanistically distinct pathways: the conventional HAT pathway and less explored radical-polar crossover pathway. This modular approach enables tuning of the reactivity by varying both acridine/LA and HAT reagent. This design strategy exhibits broad substrate scope, most importantly, exclusive C-2 selectivity of hydroetherification, hydroesterification, and hydroamination. The scope of this synthetic method was further demonstrated through late-stage modification of drug molecules, natural products, and bioactive candidates. Notably, the synthetic potential was revealed when primary alcohol reacted chemoselectively over tertiary alcohol. Furthermore, the reaction was extended to dearomative difunctionalization with excellent trans diastereoselectivity.
Source: ChemRxiv
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7151967479