Department of Chemistry, Department of Phamacology, Center for Molecular Innovation and Drug Discovery, Northwestern University, 2145 Sheridan Rd, Evanston, IL, 60208, USA.
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR, 97331, USA.
Angew Chem Int Ed Engl. 2017 Aug 7;56(33):9864-9867. doi: 10.1002/anie.201705308. Epub 2017 Jul 17.
The Armillaria and Lactarius genera of fungi produce the antimicrobial and cytotoxic mellolide, protoilludane, and marasmane sesquiterpenoids. We report a unified synthetic strategy to access the protoilludane, mellolide, and marasmane families of natural products. The key features of these syntheses are 1) the organocatalytic, enantioselective construction of key chiral intermediates from a simple achiral precursor, 2) the utility of a key 1,2-cyclobutanediol intermediate to serve as a precursor to each natural product class, and 3) a direct chemical conversion of a protoilludane to a marasmane through serendipitous ring contraction, which provides experimental support for their proposed biosynthetic relationships.
真菌属 Armillaria 和 Lactarius 产生具有抗菌和细胞毒性的麦洛内酯、原伊鲁烷和马兰烷倍半萜。我们报告了一种统一的合成策略，可获得原伊鲁烷、麦洛内酯和马兰烷天然产物家族。这些合成的关键特点是 1）从简单的非手性前体通过有机催化、对映选择性构建关键手性中间体，2）利用关键的 1,2-环丁二醇中间体作为每个天然产物类别的前体，以及 3）原伊鲁烷通过偶然的环收缩直接转化为马兰烷，这为它们提出的生物合成关系提供了实验支持。
