Usuguchi Kazuki, Takagi Akira, Takashima Ippei, Okuda Kensuke
Laboratory of Bioorganic & Natural Products Chemistry, Kobe Pharmaceutical University 4-19-1, Motoyamakita, Higashinada Kobe Hyogo 658-8558 Japan
RSC Adv. 2025 Jun 19;15(26):20734-20744. doi: 10.1039/d5ra01049g. eCollection 2025 Jun 16.
Carbasugar-containing natural products such as uvaridacol L have a variety of bioactivities, motivating chemists to develop methods for their synthesis. The conversion of -inositol is one of the most efficient methods for the synthesis of carbasugars. However, selective conversion of -inositol derivatives remains to be explored. In our synthesis of uvaridacol L derivatives, we found that the methoxy olefin derivatives of orthoester-protected -inositols, the key synthetic intermediates of our study, exhibit differing reaction selectivities depending on their geometric isomerism and substituents. Here we present new insights that contribute to the synthesis of carbasugar-type derivatives by elucidating the mechanism of the selectivity using density functional theory (DFT) calculations.
含有碳环糖的天然产物，如乌瓦里达醇L，具有多种生物活性，这促使化学家们开发其合成方法。α-肌醇的转化是合成碳环糖最有效的方法之一。然而，α-肌醇衍生物的选择性转化仍有待探索。在我们合成乌瓦里达醇L衍生物的过程中，我们发现原酸酯保护的α-肌醇的甲氧基烯烃衍生物，即我们研究的关键合成中间体，根据其几何异构和取代基的不同表现出不同的反应选择性。在此，我们通过使用密度泛函理论（DFT）计算阐明选择性机理，为碳环糖型衍生物的合成提供了新的见解。
