Ikonnikova Viktoria A, Solyev Pavel N, Al Mufti Amir M, Kungurtsev Kirill D, Korlyukov Alexander A, Baranov Mikhail S, Mikhaylov Andrey A
Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences, 16/10 Miklukho-Maklaya St., Moscow, 117997, Russia.
Engelhardt Institute of Molecular Biology of the Russian Academy of Sciences, 32 Vavilova St., Moscow, 119991, Russia.
Angew Chem Int Ed Engl. 2025 Jul 28;64(31):e202506564. doi: 10.1002/anie.202506564. Epub 2025 May 30.
Single-atom editing of complex molecules is steadily filling the chemical toolbox with site-selective modification reactions. Herein, a stepwise scheme for carbon-to-oxygen swap in tetralins leading to privileged chroman scaffolds is presented. Increasing the oxidation state at each stage, the substrate scope naturally extends: starting from tetralins via 1-tetralones and further via seven-membered lactones, the transformation results in diverse chroman-2-carboxylic acids and chroman-2-ols. The efficiency of this synthetic route is governed by the developed new oxidative ring-contractive transformations of tetrahydrobenzooxepinones, enabled by intermediate silylation into ketene acetals. The described carbon-to-oxygen swap is illustrated by 40+ examples, including skeletal editing of natural products and short formal synthesis of Heliannuol E. Formation of chroman-2-ols tentatively may proceed via original mechanism with extrusion of carbon monoxide.
复杂分子的单原子编辑正稳步地为化学工具箱增添位点选择性修饰反应。本文提出了一种用于四氢萘中碳氧交换以生成具有优势的色满骨架的分步方案。随着每一步氧化态的增加，底物范围自然扩展：从四氢萘开始，经过1-四氢萘酮，再进一步经过七元内酯，该转化反应可生成多种色满-2-羧酸和色满-2-醇。这条合成路线的效率取决于所开发的新型氧化环收缩转化反应，该反应通过中间体硅烷化生成烯酮缩醛来实现。文中通过40多个实例展示了所述的碳氧交换，包括天然产物的骨架编辑以及海链藻醇E的简短形式合成。色满-2-醇的形成可能初步通过一氧化碳挤出的原始机制进行。
