Palladium-Catalyzed Asymmetric Construction of Vicinal All-Carbon Quaternary Stereocenters and its Application to the Synthesis of Cyclotryptamine Alkaloids

A twofold Pd‐DAAA Pd‐catalyzed decarboxylative allylic alkylation (see scheme) was used to construct two vicinal all‐carbon quaternary stereocenters (marked in red) in a diastereo‐ and enantioselective fashion. The products of the Pd‐DAAA were further elaborated to complete the formal syntheses of cyclotryptamine alkaloids. The twofold Pd‐catalyzed transformation proceeds through an initial matched allylation followed by a second mismatched allylation to deliver the desired product.