American Chemical Society
ja405547f_si_001.pdf (6.03 MB)

Enantioselective Total Synthesis of (−)-Citrinadin A and Revision of Its Stereochemical Structure

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journal contribution
posted on 2016-02-19, 02:34 authored by Zhiguo Bian, Christopher C. Marvin, Stephen F. Martin
The first enantioselective total synthesis of (−)-citrinadin A has been accomplished in 20 steps from commercially available materials via an approach that minimizes refunctionalization and protection/deprotection operations. The cornerstone of this synthesis features an asymmetric vinylogous Mannich addition of a dienolate to a chiral pyridinium salt to set the initial chiral center. A sequence of substrate-controlled reactions, including a highly stereoselective epoxidation/ring-opening sequence and an oxidative rearrangement of an indole to furnish a spirooxindole, are then used to establish the remaining stereocenters in the pentacyclic core of (−)-citrinadin A. The successful synthesis of citrinadin A led to a revision of the stereochemical structure of the core substructure of the citrinadins.