Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan.
Org Lett. 2019 Sep 6;21(17):7134-7137. doi: 10.1021/acs.orglett.9b02703. Epub 2019 Aug 12.
The first concise and collective asymmetric total synthesis of six 14-hydroxygelsenicine-related 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.
首次通过分子内氮杂迈克尔加成反应，简便地构建了 7-氮杂双环[4.2.1]壬烷骨架，再通过分子内羟汞化-氧化策略，制备了具有 C14 位仲羟基的氧杂双环[3.2.2]壬烷环核，实现了 6 种 14-羟基歌海纳辛类生物碱，即 14-羟基歌海纳辛、14-乙酰氧基歌海纳辛、歌海夫兰宁、歌斯美伦碱 A 以及歌斯勒根丁 B 和 C 的首次简洁而又集中的非对映体全合成，并且通过 14-羟基歌海纳辛的发散转化，得到了生物相关的生物碱。
