Formal Nitrene Insertion into the ß-Vinyl C-H Bond of Acroleins: Synthesis of Enaminals.

An efficient formal nitrene insertion reaction into the ß-vinyl C-H bond of acroleins with an electron-rich organic azide was developed. The reaction protocol can produce secondary enaminals in high yield with a broad substrate scope. In the reaction, acid mediated [3 + 2] cycloaddition of organic azides with an acrolein generated intermediate protonated triazolines, which were selectively decomposed into enaminals with addition of a weakly Brønsted basic reagent such as methanol. The resulting secondary enaminal could be easily reduced into a γ-amino alcohol under mild hydrogenation conditions.