Minisci C−H Alkylation of Heteroarenes Enabled by Dual Photoredox/Bromide Catalysis in Micellar Solutions**

Abstract

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.

The Photoinduced Electrocyclization Reaction of Triphenylamine (TPA) in Sustainable and Confined Micellar Solutions: A Steady‐State and Laser Flash Photolysis Approach

“…[2][3][4][5][6][7] In this context, an impressive range of both photochemical and photocatalyzed processes has been investigated under micellar conditions including, among the most recent examples, photo-Fries rearrangements, [8,9] decarboxylation of αarylpropionic esters [10] and photoredox catalyzed processes. [11][12][13][14][15][16] A significant attention has been also given to the use of photocyclizations as reaction model to investigate micellar systems, as an example, the conversion of 2-pyridylphenyl ketone into fluorenone-like derivatives was investigated in sodium dodecyl sulfate and Triton X-100 micelles by Favaro and co-workers, via both steady-state and time-resolved analyses [17] More recently, Petrov and co-workers described the photochromism of 7,4'-Dihydroxyflavylium/trans-chalcone system in the presence of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as the surfactant. Interestingly, while cyclization of the chalcone derivative occurs at the hydrophobic side of the AOT reverse micelle interface, the generated flavylium ion move to the water pool, where the retro-cyclization slowly occurs.…”

Micellar photocatalysis enables divergent C-H arylation and N dealkylation of benzamides via N-acyliminium cations

“…Our previous reports, [19][20][21][22] as well as the work of others, [23][24][25][26][27] showed that micellar photocatalysis is an attractive tool for the activation of stable chemical bonds under mild reaction conditions. It can improve selectivity of processes and prolong the lifetimes of highly energetic intermediates by pre-organizing the components in the reaction mixture.…”

Chemodivergence made possible by micellar photocatalysis: C-H arylation vs. N-dealkylation of chlorinated benzamides in aqueous media

“…[17,18] We wished to achieve target reactivity through initial C-Cl activation followed by intramolecular 1,5 hydrogen-atom transfer (1,5-HAT). [19] Our previous reports, [29][30][31] as well as the work of others, [32][33][34][35][36] showed that micellar photocatalysis is an attractive tool for the activation of stable organic halides. It enables pre-organization of the components in the reaction mixture and provides high hydration energy of the released halide anions.…”