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


  • We thank the NSF (CHE-1145236) and the NIH (GM 033049) for their generous support of our programs. M.O. thanks The John Stauffer Memorial Fellowship and Stanford Graduate Fellowship for financial support. We thank Johnson-Matthey for their generous gifts of palladium salts.


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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.