碳正离子重排反应合成Cyclocitrinol核心骨架

Synthesis of Cyclocitrinol Skeleton via a Carbocation Rearrangement

Cyclocitrinol是一类具有独特的桥环结构的天然产物,其桥环核心骨架可由高张力的降蒈烯酮开环制备得到.以商品化的19-羟基雄甾为原料,通过高烯丙基碳正离子重排反应,高效地合成了降蒈烯酮关键中间体,完成了Cyclocitrinols天然产物的核心骨架的合成.

Cyclocitrinol featured a unique bridged bicyclic skeletons, which may be constructed via SmI2-mediated reaction from a highly strained norcarenone. Herein, using commercially available 19-hydroxy-androstane as starting material, the norcarenone intermediate was synthesized via a novel homoallylic carbocation rearrangement, which was transformed into the core of cyclocitrinols.