Seven kinds of sp3 α-C–H activation/C–C formation reactions of alcohols and ethers have been reviewed in this tutorial review, from the viewpoint of both methodology and synthetic application, towards the efficiency, chemo-, regio- and stereoselectivity, catalytic system, substrate scope and mechanistic study. Section 2 describes radical-mediated α-C–H activation and addition/elimination of ethers with unsaturated (C
C and C
C) species. Sections 3–8 discuss the α-C–H activation and additions of alcohols and/or ethers with unsaturated (C
C, C
C, C
O and C
N) compounds, which involve the key processes of radical mediation, carbenoid insertion, 1,5-H-migration, oxidative dehydrogenation coupling, transfer hydrogenative coupling, and metal-mediated C
C insertion into the C–H bond.
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