Litcius/Paper detail

Iron-Catalyzed Allylic Defluorinative Ketone Olefin Coupling

Chang Zhang, Lin Wang, Hongzhang Shi, Zhiyang Lin, Chuan Wang

2022Organic Letters42 citationsDOI

Abstract

In this protocol, we demonstrate our discovery that iron is able to efficiently catalyze the reductive allylic defluorinative ketyl olefin coupling reaction between α-trifluoromethyl alkenes and unactivated ketones. This operationally simple cross-electrophile reaction circumvents the use of pre-generated organometallics and allows for the synthesis of diverse functional-group-rich tertiary gem-difluorohomoallylic alcohols through a polarity-reversed strategy. Preliminary mechanistic studies support a mechanism that proceeds through a ketyl formation/olefin insertion/β-fluoro elimination sequence.

Topics & Concepts

Allylic rearrangementChemistryKetylOlefin fiberElectrophileKetoneCatalysisCombinatorial chemistryFunctional groupTrifluoromethylMedicinal chemistryOrganic chemistryRadicalAlkylPolymerFluorine in Organic ChemistryCatalytic C–H Functionalization MethodsRadical Photochemical Reactions