Photocatalysis in aqueous micellar media has recently opened wide avenues to activate strong carbon−halide bonds. So far, however, it has mainly explored strongly reducing conditions, restricting the available chemical space to radical or anionic reactivity. Here, we demonstrate a controllable, photocatalytic strategy that channels the reaction of chlorinated benzamides via either a radical or a cationic pathway, enabling a chemodivergent C−H arylation or N-dealkylation. The catalytic system operates under mild conditions with methylene blue as a photocatalyst and blue LEDs as the light source. Factors determining the reactivity of substrates, their selectivity, and preliminary mechanistic studies are presented.
Aromatic heterocycles are omnipresent structural motifs in various natural products, pharmaceuticals and agrochemicals. This work describes ap hotocatalytic Miniscitype CÀHf unctionalization of heteroarenes with non-activated alkyl bromides. The reaction avoids stoichiometricr adical-promoters, oxidants, or acids, and is conducted using blue LEDs as the light source.T he reactive carbon-centered alkyl radicals are generated by merging the photoredox approachw ith bromidea nion co-catalysis and spatialp re-aggregation of reacting speciesi nt he micellara queous solutions.T he obtained data highlight the critical importance of microstructuring and organization of the components in the reactionmixture. Scheme1.Strategies for CÀHa lkylation of heteroarenes with non-activated alkyl bromides. SDS-sodium dodecyl sulfate.
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