Abstract
A pass of electricity (4.0 F mol -1 , constant 1.5 A current) through a cell containing β-silyl cycloalkanone 1, 2 or 10 in anhydrous methanol with NaOMe at -10°C in the anodic chamber gives the corresponding aldols with hydroxymethyl groups exclusively at the α′-position; the silicon β-destabilizing effect on the intermediate enolate ion results in high regioselectivity.