RESUMO
α-Arylation of cyclic ketones via an organophotocatalytic route has been described utilizing PXZ-TRZ, a molecule displaying thermally activated delayed fluorescence (TADF). Using this route, a plethora of cyclic ketones including cyclohexanone, cyclopentanone and even cyclooctanone can be effectively arylated with many aryl iodides or bromides under mild conditions.
RESUMO
Herein we report a density functional theory (DFT)-guided mechanistic investigation of the nitrile reduction reaction, which exhibits a solvent-dependent chemodivergence. This study reveals an interesting mechanistic picture, highlighting the exact role of a protic solvent, isopropanol, in regulating the reaction outcome. The explicit solvent effect involving polar protic isopropanol favors imine metathesis by proton hopping through stepwise addition and elimination steps and thus produces a secondary amine as the final product. In contrast, the nonpolar solvent n-hexane is incapable of facilitating the proton migration and stops the solvent-assisted imine metathesis. As a result, only primary amines are obtained as the final product. This DFT study provides a recipe for the choice of solvents that can dictate chemoselectivity in product formation.
RESUMO
Herein we describe the anion of benzo[b]phenothiazine as a super reductant species upon excitation by visible light. In contrary to N-substituted phenothiazines or benzophenothiazines, this molecule holds extreme reducing power to promote single electron transfer-based reductive cleavage at a potential of -3.51 V vs SCE. As a proof, a plethora of aryl chloride substrates have been reductively cleaved to fabricate molecules of the class isoindolinone and oxindole. Moreover, an aryl-chloride bond has been homolytically cleaved to generate aryl radicals that have been utilized for C-C cross-coupling or C-P bond formation reactions. To prove its extreme reducing ability, some of the aryl fluoride bonds have been cleaved to generate aryl radicals. A detailed photophysical study including steady-state and time-resolved spectroscopic techniques explain the molecule's behavior upon light excitation, and that correlates with its reactivity pattern. Theoretical calculations disclose the benzophenothiazine anion to be slightly puckered at the ground state as the molecule is antiaromatic in nature. In contrast, the excited-state geometry is planar, which is also close to that of the intermediate after one electron transfer. Abating the antiaromaticity of the anionic species is partially responsible for its highly reducing behavior.
