Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical reactions in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation of side‐products. In this context, transition metal catalyzed reactions of onium ylides generated via diazo precursors and nucleophiles with a third component (an electrophile) have garnered significant attention. Using an allylic precursor as the electrophilic partner provides opportunities to construct all‐carbon quaternary centres. Furthermore, the presence of an allyl fragment in the multicomponent product serves as a pivotal handle for carrying out subsequent modifications. Several recent studies have employed Rh, Pd, and dual Rh/Pd catalytic systems in multicomponent reactions involving allylic alkylation that proceed via a synergistic or relay pathway. Although not significantly successful, in a few cases, asymmetric induction is achieved through chiral phosphoric acids or chiral phosphine ligands. Limited substrate and catalyst scope and the underlying mechanistic complexities have posed formidable challenges, slowing the advancement of asymmetric reactions. This review provides details of multicomponent reactions using readily available substrates like diazo compounds, allylic carbonates, and nucleophiles (R‐OH, R‐NH 2 , , etc .) forming complex organic compounds. Our primary objective is to discuss the mechanistic issues that may facilitate the progress in asymmetric reactions in this field.