仙茅内酯的全合成——第54届国际化学奥林匹克试题第9题解析  

Total Synthesis of Capitulactone:Analysis of Problem 9 of the 54th International Chemistry Olympiad

作　　者：王彦广[1] 吕萍[1] Yanguang Wang;Ping Lu(Department of Chemistry,Zhejiang University,Hangzhou 310027,China)

机构地区：[1]浙江大学化学系,杭州310027

出　　处：《大学化学》2022年第12期52-57,共6页University Chemistry

摘　　要：第54届国际化学奥林匹克试题第9题描述了仙茅内酯——一种来自于中草药大叶仙茅的天然产物的全合成。仙茅内酯的分离提取和全合成是由中国科学院上海药物研究所岳建民院士于2019年报道的研究成果。这道题由两部分组成,第一部分内容涉及仙茅内酯骨架的构筑,第二部分内容涉及由手性源D-甘露醇引入手性中心。有趣的是环状缩酮保护的D-甘露醇经氧化断裂生成了单一的手性产物,而且在后续所有转化中这个手性中心都保持下来。本题考查的主要知识点包括亲电取代反应、亲核取代反应、氧化反应、还原反应、醚键的断裂、环氧的开环、缩酮的形成等基本有机反应,此外还涉及羟基的保护与脱保护等有机合成策略。The problem 9 of the 54th International Chemistry Olympiad describes the total synthesis of capitulactone which was isolated from a plant called Curculigo capitulate,a Chinese medicinal herb.Isolation and synthesis of Capitulactone were reported by academician Jian-Min Yue of Shanghai Institute of Materia Medica in 2019.This problem comprises of two parts.The first part is the construction of the skeleton of this natural product,and the second part is the introduction of the stereocenter derived from chiral pool D-mannitol.The interesting thing is that the oxidative cleavage of the protected D-mannitol leads to a single chiral product,and the stereocenter remains neatly during all transformations.The fundamental knowledges examined in this problem include a number of classical organic reactions like electrophilic substitution,nucleophilic substitution,oxidation,reduction,cleavage of ester bond,ring-opening of epoxides,and formation of ketals.Furthermore,protection and deprotection of hydroxyl groups are also involved in this problem.

关 键 词：仙茅内酯 天然产物 全合成 中草药 

分 类 号：G64[文化科学—高等教育学] O6[文化科学—教育学]