Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
J Org Chem. 2022 Aug 5;87(15):10216-10228. doi: 10.1021/acs.joc.2c01189. Epub 2022 Jul 18.
Trifluoromethylation of furfural using the Ruppert-Prakash reagent (TMSCF) and subsequent photo-Achmatowicz reaction afforded 6-hydroxy-2-(trifluoromethyl)-2-pyran-3(6)-one. After acetylation, the resultant 6-acetoxy-2-(trifluoromethyl)-2-pyran-3(6)-one was transformed into various 1-(trifluoromethyl)-8-oxabicyclo[3.2.1]oct-3-en-2-one derivatives through a base-mediated oxidopyrylium [5 + 2] cycloaddition. The reactivity and selectivity of the 2-trifluoromethylated oxidopyrylium species toward [5 + 2] cycloaddition were analyzed using density functional theory calculations.
使用 Ruppert-Prakash 试剂（TMSCF）对糠醛进行三氟甲基化，随后进行光-Achmatowicz 反应，得到 6-羟基-2-(三氟甲基)-2-吡喃-3(6)-酮。乙酰化后，得到的 6-乙酰氧基-2-(三氟甲基)-2-吡喃-3(6)-酮通过碱介导的氧化吡喃鎓[5 + 2]环加成转化为各种 1-(三氟甲基)-8-氧杂双环[3.2.1]辛-3-烯-2-酮衍生物。使用密度泛函理论计算分析了 2-三氟甲基化氧化吡喃鎓物种对[5 + 2]环加成的反应性和选择性。
