Photochemical, Nickel-Catalyzed C(sp<sup>3</sup>)–C(sp<sup>3</sup>) Reductive Cross-Coupling of α-Silylated Alkyl Electrophiles and Allylic Sulfones
Yan Xu, Muliang Zhang, Martin Oestreich
Abstract
A nickel-catalyzed C(sp3)–C(sp3) cross-electrophile coupling between α-silylated alkyl bromides and an allylic sulfone is reported. Instead of a metal as the stoichiometric reductant, this photochemical reductive process relies on a Hantzsch ester but does not require an exogenous photocatalyst. The role of the silyl group in the α-position and its stabilizing effect on the assumed carbon-centered radical intermediate is demonstrated. The functional-group tolerance is excellent, allowing for the synthesis of various homoallylic silanes.
Topics & Concepts
ElectrophileAllylic rearrangementChemistrySilanesAlkylCatalysisReductive eliminationSilylationNickelMedicinal chemistrySulfoneCoupling reactionPhotochemistryOrganic chemistrySilaneRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques