Enantioselective conjugate additions of in situ generated 2-alkoxycarbonyl-3­(2H)-furanones to three distinct types of π-electrophiles (terminal alkynones, α-bromo enones, and α-benzyl nitroalkenes) are reported. Catalysis by a nickel­(II)–diamine complex provided alkynone-derived adducts with high enantioselectivity, preferentially as the Z-isomers, and completely suppressed the undesired O-alkylation pathway. A cupreidine-based catalyst enabled extension of the enantioselective conjugate additions to α-bromo enones and α-benzyl nitroalkenes. The densely functionalized adducts that result are useful precursors to synthetic analogs of spirocyclic natural products pseurotins.