Biomimetic Total Synthesis of (±)-Doitunggarcinone A and (+)-Garcibracteatone

A full
account of our oxidative radical cyclization approach to
the synthesis of garcibracteatone and doitunggarcinone A is presented.
This includes the first enantioselective synthesis of garcibracteatone,
which allowed the absolute configuration of the natural compound to
be determined. The first synthesis of doitunggarcinone A is also described,
which confirms our reassignment of the relative configuration of this
molecule. Novel syntheses of monoterpene fragments used to construct
the target molecules are also reported.

本研究完整报道了基于氧化自由基环化（oxidative radical cyclization）策略合成藤黄苞酮（garcibracteatone）与杜通藤黄菌素A（doitunggarcinone A）的全部工作。其中涵盖了藤黄苞酮的首次对映选择性合成（enantioselective synthesis），借此明确了该天然产物的绝对构型（absolute configuration）。本研究同时完成了杜通藤黄菌素A的首次全合成，验证了我们对该分子相对构型（relative configuration）的重新指派。此外，本文还报道了用于构建目标分子的单萜片段（monoterpene fragments）的新颖合成方法。