Asymmetric, Remote C(sp<sup>3</sup>)−H Arylation via Sulfinyl‐Smiles Rearrangement
Yawen Hu, Cédric Hervieu, Estı́baliz Merino, Cristina Nevado
Abstract
)-H bonds under photoredox conditions is described here. The reaction features the addition radicals to a double bond followed by a site-selective radical translocation (1,n-hydrogen atom transfer) as well as a stereocontrolled aryl migration via sulfinyl-Smiles rearrangement furnishing a wide range of chiral α-arylated amides with up to >99 : 1 er. Mechanistic studies indicate that the sulfinamide group governs the stereochemistry of the product with the aryl migration being the rate determining step preceded by a kinetically favored 1,n-HAT process.
Topics & Concepts
Smiles rearrangementChemistryRadicalArylHydrogen atomStereochemistryAryl radicalHydrogen bondPhotochemistrySulfoneMedicinal chemistryGroup (periodic table)MoleculeOrganic chemistryAlkylCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques