Biomimetic Cationic Cyclization toward ent-Kaurene-type Diterpenoids

作     者：Lili Zhu Ran Hong 

作者机构：CAS Key Laboratory of Synthetic Chemistry of Natural Substances Shanghai Institute of Organic Chemistry Chi- nese Academy of Sciences Shanghai 200032 China 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：2013年第31卷第1期

页      面：111-118页

核心收录：

学科分类：1007[医学-药学(可授医学、理学学位)] 08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 10[医学] 

基　　金：国家973计划 中国科学院项目 

主　　题：diterpenoid ent-kaurene biomimetic synthesis carbocation cyclization Birch reduction/alkylationcascade 

摘      要：Terpenoids comprise the largest family of natural products and include various structurally different genus which play important roles in living organisms. Biosynthetically, diterpenoids are derived from （E,E,E）-geranylgeranyl diphosphate （GGPP）. From GGPP, diterpene cyclase catalyzes a sequence of carbocation- mediated cyclizations, rearrangements, and further oxidations, leading to a class of structurally unique ent-kaurenes, such as cafestol, gibberellin A3 and oridonin. According to the biosynthesis pathway of ent-kaurene, we designed a chiral acetal-enabled and SnCln-promoted biomimetic polyene cationic cyclization. With a following Birch reduc- tiort/alkylation cascade, a core skeleton of representative ent-kaurenes diterpenoids was completed.