Anomeric C-H bond activation is an unsolved long-standing synthetic challenge. Herein we report a diastereoselective Pd-catalyzed anomeric C(sp 3 )-H activation methodology that allows the synthesis of elusive C-(hetero)arylglycosides with an exclusive α-selectivity.a Reactions were performed an oven dried re-sealable tube using sugar 1a (0.1 mmol), ArX 2 (3 equiv), Pd(OAc)2 (0.01 mmol), Ag2CO3 (3 equiv) in tAmOH (1.0 mL) at 120 °C. b Yield of isolated product.

Transition‐metal‐catalyzed C−H functionalization and photoredox nickel dual catalysis have emerged as innovative and powerful avenues for the synthesis of C‐branched glycosides. These two concepts have been recently established and provide efficient and mild methods for accessing a series of valuable complex C‐branched glycosides of great interest. Herein, recent developments in the synthesis of C‐branched aryl/alkenyl/alkyl glycosides through these two approaches are highlighted.