High 1, 2-asymmetric induction was realized by the addition of a 1-hydroxy-1-methylethyl radical to conformationally flexible (E)-γ-hydroxy α, β-unsaturated carboxylic esters and sulfones (1 and 2, respectively). Upon the irradiation (> 290 nm) of (E)-1 and benzophenone in 2-propanol, the 1-hydroxy-1-methylethyl radical was generated in situ and added to (E)-1 with high anti-stereoselectivity. The bulkier is the γ-alkyl group of (E)-1, the higher does ...