Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, C1428EGA, Buenos Aires, Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)-UBA, Centro de Investigación en Hidratos de Carbono (CIHIDECAR), C1428EGA, Buenos Aires, Argentina.
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, C1428EGA, Buenos Aires, Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)-UBA, Centro de Investigación en Hidratos de Carbono (CIHIDECAR), C1428EGA, Buenos Aires, Argentina.
Carbohydr Res. 2019 Sep 1;483:107751. doi: 10.1016/j.carres.2019.107751. Epub 2019 Jul 24.
A 6-azido-2-tosylenolate, obtained from D-glucono-1,5-lactone in six steps, underwent an intramolecular cycloaddition-elimination pathway under mild conditions, yielding a chiral, substituted 5,6-dihydro-4H-pyrrolo[1,2-c]-1,2,3-triazole. The conditions were optimized to give exclusive formation of the triazole. The mechanism appears to involve intramolecular ring closure via a 1,3-dipolar azide-alkene cycloaddition to give a 1,2,3-triazoline, followed by elimination of p-toluenesulfonic acid, leading to aromatization. Triazole products, obtained by chemical modification, are expected to display activity as enzyme inhibitors. Furthermore, partially protected derivatives of the 2-hexenoate were prepared as useful synthetic intermediates.
一种 6-叠氮-2-对甲苯磺酸盐，由 D-葡萄糖-1,5-内酯经六步反应制得，在温和条件下通过分子内环加成-消除途径反应，得到手性取代的 5,6-二氢-4H-吡咯并[1,2-c]-1,2,3-三唑。优化了反应条件以得到三唑的专一性形成。该反应机制似乎涉及通过 1,3-偶极氮丙啶-烯烃环加成进行分子内环化，生成 1,2,3-三唑啉，然后消除对甲苯磺酸，导致芳构化。通过化学修饰获得的三唑产物有望作为酶抑制剂发挥作用。此外，还制备了 2-己烯酸的部分保护衍生物，作为有用的合成中间体。
