College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China.
Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, Shanghai 200237, China.
J Org Chem. 2021 Dec 3;86(23):16940-16947. doi: 10.1021/acs.joc.1c02099. Epub 2021 Nov 2.
Carboxylic acids are widely found in natural products and bioactive molecules and have served as raw material compounds in industry. We now report the first example of copper(I)-catalyzed carboxyl transfer annulation of propiolic acids with amines, thereby chemodivergently constructing the oxazolidine-2-ones. In this reaction, two kinds of key propargyamine intermediates were formed through sequential CuI/NBS-catalyzed oxidative deamination/decarboxylative alkynylation or CuI-catalyzed decarboxylative hydroamination/alkynylation. The advantages of this decarboxylative coupling/carboxylative cyclization are showcased in the atom economy, chemical specificity, and functional group tolerance.
羧酸广泛存在于天然产物和生物活性分子中，并且一直是工业中作为原料化合物使用。我们现在报告了第一个铜（I）催化丙炔酸与胺的羧基转移环化反应的例子，从而通过化学选择性构建了恶唑烷-2-酮。在该反应中，通过顺序 CuI/NBS 催化的氧化脱氨/脱羧基炔基化或 CuI 催化的脱羧基氨化/炔基化形成两种关键的丙炔胺中间体。这种脱羧偶联/羧基环化的优点在于原子经济性、化学特异性和官能团耐受性。
