Rh(II)/Pd(0) Dual-Catalyzed Regio-Divergent Three-Component Propargylic Substitution

[Image: see text] Regio-divergent propargylic substitution to generate functionally diverse products from identical starting materials remains a formidable challenge, probably due to the unpredictable regiochemical complexity. In practically, the synthesis of α-quaternary propargylic-substituted products is still much less developed, and preprepared nucleophiles are generally applied in this type of reaction with propargylic substrates, which limits the reaction efficiency and diversity of the obtained products. Herein, we disclose unprecedented three-component propargylic substitution of α-diazo esters with amines and propargylic carbonates under dirhodium/palladium dual catalysis. The key to the success of this multicomponent propargylic substitution is to avoid two-component side reactions through a tandem process of dirhodium(II)-catalyzed carbene insertion and palladium-catalyzed regiodivergent propargylic substitution. The judicious selection of a diphosphine (dppf) or monophosphine ((t)BuBrettphos) as the ligand is crucial for the reaction to generate different products in a switchable way, α-quaternary 1,3-dienyl or propargylated products, with high regio- and chemoselectivities.