Photoredox-Catalyzed Allylic Defluorinative Alkoxycarbonylation of Trifluoromethyl Alkenes through Intermolecular Alkoxycarbonyl Radical Addition
Jiaxin Wang, Wei Ge, Ming‐Chen Fu, Yao Fu
Abstract
The gem-difluoroalkene moiety is an ideal carbonyl bioisostere in medicinal chemistry, but efficient synthesis of β-gem-difluoroalkene esters remains challenging so far. Herein, we disclose a photoredox-catalyzed allylic defluorinative alkoxycarbonylation of trifluoromethyl alkenes enabled by intermolecular alkoxycarbonyl radical addition. A wide variety of alcohol oxalate derivatives were amenable, affording various β-gem-difluoroalkene esters with excellent functional group tolerance. Notably, the potential synthetic value of this method is highlighted by successful late-stage modification for bioactive molecules.
Topics & Concepts
ChemistryTrifluoromethylMoietyAllylic rearrangementIntermolecular forcePhotoredox catalysisCatalysisOxalateCombinatorial chemistryAlcoholBioisostereOrganic chemistryMedicinal chemistryMoleculeChemical synthesisAlkylIn vitroPhotocatalysisBiochemistryFluorine in Organic ChemistryRadical Photochemical ReactionsInorganic Fluorides and Related Compounds