Synthesis of Vinca Alkaloids and Related Compounds. Part XCIII. Skeletal Rearrangement of Cyclovinblastine Derivatives: Formation of a Novel Bisindole System

HETEROCYCLES
1999.0

Abstract

Bisindole alkaloids of the vinblastine (VLB) type can be oxidized to give a Ψ-aspidosperma-aspidosperma type skeleton via 3'-7'-transannular cyclization. Acid catalysis triggers an aspidospermane→eburnane skeletal rearrangement of these cyclic derivatives, thus giving a novel bisindole system with a Ψ-eburnea-aspidosperma type skeleton. A previously unexplored aspect of this transformation is the observed retention or inversion at C(16') depending on the starting C(16') configuration. The present paper gives a detailed account of the synthetic aspect of this work together with preliminary NMR and CD results concerning the epimerization at C(16').

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