Synthesis of Chroman Derivatives by Group Transposition and Atom Swapping in 1‐Tetralones: Single‐Atom Editing Enabled by Oxidative Ring Contraction of Benzoxepine Silyl Ketene Acetals
Abstract
Abstract 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.
Article Details
Authors (7)
Viktoria A. Ikonnikova
Institute of Chemical Research of Catalonia (ICIQ‐CERCA) The Barcelona Institute of Science and Technology Av. Països Catalans 16 Tarragona 43007 Spain
Pavel N. Solyev
Engelhardt Institute of Molecular Biology of the Russian Academy of Sciences 32 Vavilova St. Moscow 119991 Russia
Amir M. Al Mufti
Shemyakin‐Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences 16/10 Miklukho‐Maklaya St. Moscow 117997 Russia
Kirill D. Kungurtsev
Shemyakin‐Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences 16/10 Miklukho‐Maklaya St. Moscow 117997 Russia
Alexander A. Korlyukov
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences 28 Vavilova Street Moscow 119334 Russia
Mikhail S. Baranov
Shemyakin‐Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences 16/10 Miklukho‐Maklaya St. Moscow 117997 Russia
Andrey A. Mikhaylov
Shemyakin‐Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences 16/10 Miklukho‐Maklaya St. Moscow 117997 Russia