We report that nitrogen heterocycles can serve as competent nucleophiles in the palladiumcatalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines. The resulting alkylated products were obtained with high regio-, chemo-, and enantioselectivity. Both substituted 1H-pyrroles and 1H-indoles were successfully employed to give exclusively the branched N-alkylated products. The synthetic utility of this process was demonstrated by applying this method to the preparation of several medicinal chemistry lead compounds and bromopyrrole alkaloids including longamide B, longamide B methyl ester, hanishin, agesamides A and B, and cyclooroidin.
We report the use of a two-fold Pd-catalyzed decarboxylative allylic alkylation (Pd-DAAA) to construct two vicinal all carbon quaternary stereocenters in a diastereo- and enantioselective fashion. To demonstrate the synthetic utility of this process, the products of the Pd-DAAA were elaborated to complete the formal syntheses of the cyclotryptamine alkaloids. Mechanistic investigations have revealed that the two-fold Pd-catalyzed transformation proceeds through an initial matched first allylation followed by a second mismatched allylation to deliver the desired product.
We report the discovery, synthesis, and application of a new class of non-C2-symmetric phosphoramidite ligands derived from pyroglutamic acid for use in both oxidative and redox-neutral palladium-catalyzed asymmetric allylic alkylations of 1,3-diketones. The resulting chiral products are typically obtained in high yield with good to excellent levels of enantioselectivity.
The communesin alkaloids are a diverse family of Penicillium-derived alkaloids. Their caged-polycyclic structure and intriguing biological profiles have made these natural products attractive targets for total synthesis. Similarly, the ascidian-derived alkaloid, perophoramidine, is structurally related to the communesins and has also become a popular target for total synthesis. This review serves to summarize the many elegant approaches that have been developed to access the communesin alkaloids and perophoramidine. Likewise, strategies to access the communesin ring system are reviewed.
We describe a catalytic asymmetric total synthesis of the ascidian alkaloid (–)-perophoramidine employing a Mo-catalyzed asymmetric allylic alkylation and unprecedented imino ether allylation as key steps.
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