Three chapters: I. Metallophosphite-induced nucleophilic acylation of α, β-unsaturated amides: facilitated catalysis by a diastereoselective retro-[1,4]-brook rearrangement. II. Metallophosphite-catalyzed asymmetric acylation of α, β-unsaturated amides. III. Enantioselective metallophosphite-catalyzed acylation of nitrones to yield [N]silyloxy- α-amino ketones.