Daphnezomines A和B的四环核心骨架合成

Synthesis of Tetracyclic Core Structure of Daphnezomines A and B

在虎皮楠生物碱家族中, daphnezomine A型生物碱仅包含三位成员:daphnezomine A (1), daphnezomine B (2)以及dapholdhamineB.这些生物碱含有独特的氮杂金刚烷骨架,9个连续的手性立体中心,因此呈现出巨大的合成挑战性.报道了分子1和2的四环核心骨架的合成.关键步骤包括一个黄氏酰胺活化增环反应和一个Hutchins-Kabalka还原重排反应.

Among the tiniest Daphniphyllum alkaloid subfamilies, daphnezomine A-type alkaloids consist of only three known members, namely daphnezomine A(1), daphnezomine B(2) and dapholdhamine B. These alkaloids contain a unique aza-adamantane core along with nine contiguous stereogenic centers, thus presenting remarkable synthetic challenges. The synthesis of tetracyclic core structure of 1 and 2 was reported. The key steps in our approach include a Huang’s amide-activa tion-annulation and a Hutchins-Kabalka reductive rearrangement.