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Total Synthesis of (-)-14-Hydroxygelsenicine and Six Biogenetically Related Gelsemium Alkaloids
Atsushi Saito1, Noriyuki Kogure1, Mariko Kitajima1
1Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan.
Abstract:
The first concise and collective asymmetric total synthesis of six 14-hydroxygelsenicine-related Gelsemium alkaloids, i.e., 14-hydroxygelsedilam, 14-acetoxygelsedilam, gelsefuranidine, gelsemolenine A, and gelselegandines B and C, was accomplished via the facile construction of a 7-azabicyclo[4.2.1]nonane skeleton by intramolecular aza-Michael addition, the preparation of an oxabicyclo[3.2.2]nonane ring core with a secondary hydroxy group at C14 by an intramolecular oxymercuration-hydroxylation strategy, and divergent transformations of 14-hydroxygelsenicine into biogenetically related alkaloids.
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