Affiliation:
1. Key Laboratory of Medicinal Chemistry for Natural Resource Ministry of Education Yunnan Provincial Center for Research and Development of Natural Products Yunnan Characteristic Plant Extraction Laboratory School of Pharmacy Yunnan University Kunming 650091 P. R. China
Abstract
AbstractKopsiaalkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all‐carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α‐hydroxyketone moiety, and a bioinspired retro‐Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.
Funder
National Natural Science Foundation of China
National Key Research and Development Program of China