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Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for the Enantioselective Total Synthesis of Mavacuran Alkaloids

preprint
submitted on 26.04.2019 and posted on 30.04.2019 by Maxime Jarret, Victor Turpin, Aurélien Tap, Jean-Francois Gallard, Cyrille Kouklovsky, Erwan Poupon, Guillaume Vincent, Laurent Evanno
We report the enantioselective total syntheses of mavacurans alkaloids, (+)-taberdivarine H, (+)-16-hydoxymethyl-pleiocarpamine, (+)-16-epi-pleiocarpamine, and their postulated biosynthetic precursor 16-formyl-pleiocarpamine. This family of monoterpene indole alkaloids is a target of choice since some of its members are subunits of intricate bisindole alkaloids such as bipleiophylline. Inspired by the biosynthetic hypothesis, we explored an oxidative coupling approach from the geissoschizine framework to form the N1-C16 bond. Quaternization of the aliphatic nitrogen was key to achieve the oxidative coupling induced by KHMDS/I2 since it hides the nucleophilicity of the aliphatic nitrogen and locks the required cis conformation.

Funding

ANR (ANR-15-CE29-0001; “Mount Indole”)

History

Email Address of Submitting Author

guillaume.vincent@u-psud.fr

Institution

Univ Paris-Sud, CNRS, Univ Paris Saclay

Country

France

ORCID For Submitting Author

0000-0003-3162-1320

Declaration of Conflict of Interest

no conflict of interest

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