Abstract We developed a novel method for the synthesis of 2‐substituted‐4,5‐dihydrothiazol‐4‐ols compounds through cyclization of thioamides and 1,4‐dithiane‐2,5‐diol in the presence of Et 3 N. Stable hydroxy‐substituted thiazole compounds were isolated of substituted thioamides. The reaction conditions are simple, the substrate range is wide, and the target compounds were obtained in up to 82 % yield.