AbstractThe first metal‐catalyzed 1,4‐selective asymmetric addition of malonates to nitroenynes promoted by a simple chiral nickel(II)‐diamine catalyst, was developed, facilitating a mild synthesis of a novel type of multifunctional chiral β‐alkynyl acids bearing a nitro group. Based on this protocol, we have developed a practical and collective synthesis of a series of diverse functional molecules and building blocks including new types of chiral β‐alkynyl‐γ‐amino acids, β‐functionalized chiral δ‐keto‐γ‐lactones, chiral γ‐alkylidenelactones, alkynyl‐substituted pyrrole‐3‐carboxylic acid derivatives, tetrasubstituted furans and chiral β‐alkynyl‐γ‐lactams. Notably, we discovered two unusual tandem reactions leading to functionalized chiral 1,5‐dicarbonyl compounds. In addition, by employing simple bifunctional organocatalysts, we have developed the first regio‐, diastereo‐ and enantioselective conjugate addition of α‐substituted β‐keto esters to nitroenynes, which is poorly diastereoselective with chiral nickel(II)‐diamine catalysts, providing a new entry to adjacent quaternary and tertiary stereocenters in one step. Based on this protocol, we have developed a concise asymmetric synthesis of conformationally constrained bicyclic γ2‐amino acids featuring an alkynyl side chain with an adjacent quaternary carbon stereocenter. The study described here demonstrates that the mutually complementary strategy of transition metal catalysis and organocatalysis is a powerful and promising tool in catalytic asymmetric synthesis.