Recent Progress on Transition-Metal-Mediated Reductive C(sp3)–O Bond Radical Addition and Coupling Reactions.

In this short review, we summarize the recent developments on thermo-driven C(sp³)–O bond radical scission methods and their applications in the construction of C(sp³)–C bonds via conjugate addition with activated double bonds and reductive coupling mediated by economic 3d metals, in particular nickel. We have arranged the review based on three approaches for C(sp³)–O bond radical scission (vide infra). After generating the radical intermediates, their subsequent transformation into C(sp³)–C bonds enabled by C(sp³)–O cross-electrophile coupling with carbon electrophiles is discussed in detail. 1 Introduction 2 Direct Single-Electron Transfer to a C(sp³)–O Bond 3 Radical Scission of Activated C(sp³)–O Bonds via Single-Electron Transfer to Protecting Groups 4 In Situ Activation of Alcohols 5 Summary and Outlook [ABSTRACT FROM AUTHOR]