“…Intermediate IV experienced a H shift to produce species V. Subsequent intramolecular recombination of alkyl radicals with Cu II promoted the formation of chiral Cu III species VI. Finally, the target C(sp 3 )−C(sp 3 )−H glycosylation Scheme 3. Substrate Scope a,b,c a Reaction conditions: 1a (2 equiv, 0.2 mmol), 2a (1 equiv, 0.1 mmol), L1 (0.012 mmol, 0.12 equiv), Cu(OTf) 2 (0.1 equiv, 0.01 mmol), DABCO (1.5 equiv, 0.15 mmol), argon atmosphere, 15 h, −10 °C, and under 440 nm blue LED.…”