Department of Synthetic Organic Chemistry, Graduate School of Biomedical and Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553, Japan.
J Org Chem. 2022 Sep 16;87(18):12491-12497. doi: 10.1021/acs.joc.2c01653. Epub 2022 Aug 30.
The asymmetric total synthesis of angucycline antibiotics ()-brasiliquinones B and C was accomplished. The benz[]anthraquinone core was constructed via oxidative cyclization of a hydroquinone-silyl enol ether hybrid. The resultant pentacyclic acetal was converted to the silyl enol ether, which was treated with Pd(II)/O to afford brasiliquinone C, after multistep conversion including dehydrogenation, desilylation and deacetalization, and hydroquinone oxidation. The ()-configuration of natural brasiliquinones was confirmed based on the stereochemical correlation with the synthetic products.
不对称全合成了蒽环类抗生素（）-brasiliquinones B 和 C。苯并[ ]蒽醌核心是通过对氢醌-硅基烯醇醚杂化物进行氧化环化构建的。所得的五元环缩醛被转化为硅基烯醇醚，用 Pd(II)/O 处理得到 brasiliquinone C，经过包括脱氢、去硅和去缩醛以及氢醌氧化在内的多步转化。天然 brasiliquinones 的 ()-构型是基于与合成产物的立体化学相关性确定的。
