β-Hydroxylation of α,β-Unsaturated Ketones

Significance

A highly chemo- and enantioselective nucleophilic addition of oxime 1 to α,β-unsaturated ketones catalyzed by chiral primary amine salt 3 is reported. Different linear α,β-unsaturated ketones 2 were tested and afforded optically active products 4 in moderate to good yields and high enantioselectivities (46-56% yield, er up to 97:3). Currently the scope is limited and enones bearing aromatic or hindered β-substituents cannot be used. The synthetic utility of this new approach is presented with a reductive cleavage to β-hydroxyketones and subsequent reduction to optically active syn- or anti-1,3-diols.