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Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for the Total Synthesis of (−)‐17‐nor‐Excelsinidine
Author(s) -
Jarret Maxime,
Tap Aurélien,
Kouklovsky Cyrille,
Poupon Erwan,
Evanno Laurent,
Vincent Guillaume
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802610
Subject(s) - oxidative coupling of methane , intramolecular force , oxidative phosphorylation , chemistry , total synthesis , monoterpene , stereochemistry , indole alkaloid , indole test , combinatorial chemistry , organic chemistry , biochemistry , catalysis
Abstract We report the first total synthesis of (−)‐17‐nor‐excelsinidine, a zwitterionic monoterpene indole alkaloid that displays an unusual N4−C16 connection. Inspired by the postulated biosynthesis, we explored an oxidative coupling approach from the geissoschizine framework to forge the key ammonium–acetate connection. Two strategies allowed us to achieve this goal, namely an intramolecular nucleophilic substitution on a 16‐chlorolactam with the N4 nitrogen atom or a direct I 2 ‐mediated N4−C16 oxidative coupling from the enolate of geissoschizine.