Mrinmoy Saha - Unified Synthesis of 10-Oxygenated Lycopodium Alkaloids: Impact of C10-Stereochemistry on Reactivity

Version 2

      Publication Details (including relevant citation   information):

      J. Org. Chem.

      Abstract:

        The pronounced impact of the C10 stereochemistry   on the successful construction of a   polycyclic Lycopodium alkaloid   scaffold has been explored. A wide range of reaction conditions   and functionality were investigated to control a keto sulfone   Michael addition to construct the C7–C12linkage.   An unexpected, overriding impact of the C10 stereochemistry   in stereoselectivity and reaction rate in the Michael addition   was observed. Furthermore, divergent reactivity of a   conformationally accelerated, intramolecular Mannich cyclization   based on the C10stereochemistry   was discovered. The successful execution of this synthetic route   resulted in the total synthesis of all three known   10-oxygenated Lycopodium alkaloids:   10-hydroxylycopodine, paniculine, and deacetylpaniculine.

      Address (URL): http://pubs.acs.org/doi/abs/10.1021/acs.joc.6b00900