Department of Natural Products Chemistry, Key Lab of Chemical Biology, School of Pharmaceutical Sciences, Shandong University, Jinan, 250012, China.
School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.
Angew Chem Int Ed Engl. 2021 Jul 5;60(28):15286-15290. doi: 10.1002/anie.202104182. Epub 2021 Jun 7.
An enantioselective synthetic approach for preparing manginoids and guignardones, two types of biogenetically related meroterpenoids, is reported. This bioinspired and divergent synthesis employs an oxidative 1,3-dicarbonyl radical-initiated cyclization and cyclodehydration of the common precursor to forge the central ring of the manginoids and guignardones, respectively, at a late stage. Key synthetic steps include silica-gel-promoted semipinacol rearrangement to form the 6-oxabicyclo[3.2.1]octane skeleton and the Suzuki-Miyaura reaction of vinyl bromide to achieve fragment coupling. This synthesis protocol enables the asymmetric syntheses of four fungal meroterpenoids from commercially available materials.
本文报道了一种对映选择性合成方法，用于制备两种生物相关的混合萜类化合物——曼尼希碱和吉尼亚酮。这种受生物启发的发散合成方法在后期使用氧化 1,3-二羰基自由基引发的环化和环脱水反应，分别构建曼尼希碱和吉尼亚酮的中环。关键的合成步骤包括硅胶促进的半频哪醇重排形成 6-氧杂双环[3.2.1]辛烷骨架和乙烯基溴的铃木-宫浦反应实现片段偶联。该合成方案能够从商业可得的原料中进行四种真菌混合萜类化合物的不对称合成。
