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Photoinduced 1,2-dicarbofunctionalization of alkenes with organotrifluoroborate nucleophiles<i>via</i>radical/polar crossover

María Jesús Cabrera‐Afonso, Anasheh Sookezian, Shorouk O. Badir, Mirna El Khatib, Gary A. Molander

2021Chemical Science77 citationsDOIOpen Access PDF

Abstract

-(acyloxy)phthalimide redox-active esters as radical progenitors and organotrifluoroborates as carbon-centered nucleophiles is reported. This redox-neutral, multicomponent reaction is postulated to proceed through photochemical radical/polar crossover to afford a key carbocation species that undergoes subsequent trapping with organoboron nucleophiles to accomplish the carboallylation, carboalkenylation, carboalkynylation, and carboarylation of alkenes with regio- and chemoselective control. The mechanistic intricacies of this difunctionalization were elucidated through Stern-Volmer quenching studies, photochemical quantum yield measurements, and trapping experiments of radical and ionic intermediates.

Topics & Concepts

ChemistryNucleophileCarbocationAlkenePhotochemistryQuenching (fluorescence)RadicalHydridePhthalimideElectrophileRedoxCombinatorial chemistryOrganic chemistryHydrogenPhysicsQuantum mechanicsCatalysisFluorescenceRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques
Photoinduced 1,2-dicarbofunctionalization of alkenes with organotrifluoroborate nucleophiles<i>via</i>radical/polar crossover | Litcius