Biomimetic Cationic Cyclization toward ent-Kaurene-type Diterpenoids  

作　　者：Lili Zhu Ran Hong 

机构地区：[1]CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chi- nese Academy of Sciences, Shanghai 200032, China

出　　处：《Chinese Journal of Chemistry》2013年第1期111-118,共8页中国化学（英文版）

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.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.

关 键 词：DITERPENOID ent-kaurene biomimetic synthesis carbocation cyclization Birch reduction/alkylationcascade 

分 类 号：TQ463[化学工程—制药化工] TQ333.1