Bioinspired Total Syntheses of Grayanotoxins II/III,Kalmanol,and Rhodomollacetals A–C with Three Distinct Skeletons  

作　　者：Hao Cheng Tianhao Ma Xiao Liu Yanxing Jia 

机构地区：[1]State Key Laboratory of Natural and Biomimetic Drugs,School of Pharmaceutical Sciences,Chemical Biology Center,Peking University,Beijing 100191

出　　处：《CCS Chemistry》2024年第11期2741-2748,共8页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation(grant nos.22331001 and 21925101)。

摘　　要：Grayanane diterpenoids,which have intricate molecular architecture and interesting pharmacological properties,have attracted considerable interest of organic chemists since 1970s.However,the total syntheses of grayanane diterpenoids have been accomplished by only seven groups,which have mainly focused on the same carbon skeleton.Herein,we disclose the bioinspired total syntheses of six grayanane diterpenoids with three distinct carbon skeletons:grayanotoxins II/III,kalmanol,and rhodomollacetals A–C.Among them,the total syntheses of rhodomollacetals A–C were achieved for the first time.The total syntheses feature a Ni-catalyzedα-vinylation ofβ-ketoester to construct a bicyclo[3.2.1]octane ring system,an intramolecular Pauson–Khand reaction of enyne to construct a 7/5-bicyclic ring system,a biomimetic 1,2-rearrangement of grayanane-type 5/7/6/5 skeleton to generate kalmane-type 5/8/5/5 skeleton,and a biomimetic oxidative cleavage of C2–C3 and C5–C6 bonds/skeletal reconstruction to construct a rhodomollacetal A skeleton.

关 键 词：DITERPENOIDS bioinspired total syntheses divergent total syntheses Ni-catalyzed intramolecular Pauson–Khand reaction 

分 类 号：O62[理学—有机化学]