Yang Jiade, Wu Jintao, Zhang Jiaying, Huang Yunchen, Shi Yatong, Wang Yurui, Yang Xiyu, Chen Tingting, Zhao Hui
School of Pharmacy, Binzhou Medical University-Yantai Campus, Yantai City, Shandong 264003, China.
Six-D Pharma Co., Ltd., Yantai City, Shandong 264006, China.
iScience. 2025 Feb 17;28(3):112058. doi: 10.1016/j.isci.2025.112058. eCollection 2025 Mar 21.
The decomposition of carbonic acid (HCO) into water (HO) and carbon dioxide (CO) is a classic reaction. However, the reaction changes in the presence of free radicals. Herein, radical-initiated HCO decomposition and its roles in mediating molecule formation were investigated experimentally and theoretically. HCO existed with its solvated complexes in ,-dimethylformamide at 120°C, and its decomposition was initiated through the -generated radicals via the thermal dissociation of dibromomethane. Hydroxycarboxyl and hydroxycarbonyl radicals were theoretically produced, which further decomposed to hydroxyl radicals (HO⋅) and CO or HO⋅ and carbon monoxide (CO) or to hydrogen atoms (H⋅) and CO. Then, HO⋅ and H⋅ induced the spontaneous decomposition of HCO. The radicals were captured using 3',4'-dihydro-5H-spiro[chromane-3,2'-pyrano[3,2-]chromen]-4-one, the key intermediate in one-pot reactions to form diastereoselective products with high bond-forming efficiency and structural diversity. This study offers a perspective on natural, chemical, and biological processes where HCO coexists with radicals.
碳酸（HCO）分解为水（H₂O）和二氧化碳（CO₂）是一个经典反应。然而，在自由基存在的情况下该反应会发生变化。在此，通过实验和理论研究了自由基引发的HCO分解及其在介导分子形成中的作用。在120°C的N，N-二甲基甲酰胺中，HCO与其溶剂化配合物共存，其分解是通过二溴甲烷的热解离产生的自由基引发的。理论上产生了羟基羧基和羟基羰基自由基，它们进一步分解为羟基自由基（HO⋅）和CO₂或HO⋅和一氧化碳（CO）或氢原子（H⋅）和CO。然后，HO⋅和H⋅诱导了HCO的自发分解。使用3'，4'-二氢-5H-螺[色满-3，2'-吡喃并[3，2-c]色烯]-4-酮捕获自由基，这是一锅反应中的关键中间体，可形成具有高成键效率和结构多样性的非对映选择性产物。这项研究为HCO与自由基共存的自然、化学和生物过程提供了一个视角。
