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.

本研究详细报道了我们采用氧化自由基环化策略合成藤黄二烯酮（garcibracteatone）与都东藤黄酮A（doitunggarcinone A）的完整工作。其中首次实现了藤黄二烯酮的对映选择性合成，借此确定了该天然产物的绝对构型。同时首次完成了都东藤黄酮A的全合成，验证了我们对该分子相对构型的重新指定。此外还报道了用于构建目标分子的单萜片段的新型合成方法。