Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for Enantioselective Total Synthesis of Mavacuran Alkaloids
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Authors: | Maxime Jarret,Victor Turpin,Aur lien Tap,Jean‐Fran ois Gallard,Cyrille Kouklovsky,Erwan Poupon,Guillaume Vincent,Laurent Evanno |
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Affiliation: | Maxime Jarret,Victor Turpin,Aurélien Tap,Jean‐François Gallard,Cyrille Kouklovsky,Erwan Poupon,Guillaume Vincent,Laurent Evanno |
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Abstract: | Reported is the enantioselective total syntheses of mavacuran alkaloids, (+)‐taberdivarine H, (+)‐16‐hydroxymethyl‐pleiocarpamine, and (+)‐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, an oxidative coupling approach from the geissoschizine framework to form the N1?C16 bond was explored. Quaternization of the aliphatic nitrogen center was key to achieving the oxidative coupling induced by KHMDS/I2 as it masks the nucleophilicity of the aliphatic nitrogen center and locks in the required cis conformation. |
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Keywords: | Alkaloide Biosynthese Naturstoffe Oxidationen Totalsynthese |
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