From Racemic to Enantioselective Total Synthesis of Trigonoliimines via Development of an Organocatalytic Enantioselective Michael Addition of α-Aryl-α-isocyanoacetate to Vinyl Phenyl Selenone

Authors

  • Thomas Buyck Laboratory of Synthesis and Natural Products Institute of Chemical Sciences and Engineering Ecole Polytechnique Fédérale de Lausanne EPFL-SB-ISIC-LSPN, CH-1015 Lausanne, Switzerland
  • Qian Wang Laboratory of Synthesis and Natural Products Institute of Chemical Sciences and Engineering Ecole Polytechnique Fédérale de Lausanne EPFL-SB-ISIC-LSPN, CH-1015 Lausanne, Switzerland
  • Jieping Zhu Laboratory of Synthesis and Natural Products Institute of Chemical Sciences and Engineering Ecole Polytechnique Fédérale de Lausanne EPFL-SB-ISIC-LSPN, CH-1015 Lausanne, Switzerland. jieping.zhu@epfl.ch

DOI:

https://doi.org/10.2533/chimia.2014.211

Keywords:

Asymmetric michael addition, Bisindole alkaloid, Natural product, Organocatalysis, Selenium, Trigonoliimines

Abstract

Trigonoliimines are hexacyclic bisindole alkaloids isolated recently by Hao and co-workers. A synthesis of (±)-trigonoliimine B was accomplished in seven steps from simple starting materials featuring the Bischler-Napieralski reaction for closing the seven-membered ring with concomitant formation of an exoimine. Sulfolane was found to be the solvent of choice for this unprecedented transformation. An organocatalytic enantioselective synthesis of α,α'-disubstituted α-amino acids was subsequently developed using methyl α-aryl-α-isocyanoacetates as glycine templates and vinyl phenyl selenone as a Michael acceptor. Using one of this Michael adducts as a starting material, total synthesis of both (+)- and (–)-trigonoliimine A was subsequently realized.

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Published

2014-04-30

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