Synthesis of Amino‐ and Hydroxymethyl Benzoxaboroles: Prominent Scaffolds for Further Functionalization

Herein, we describe the development of a short, simple, and efficient synthesis of amino‐ and hydroxymethyl‐substituted benzoxaboroles. The key step in our strategy was the early stage incorporation of the boron by the borylation of an aniline. The formed boronates were then elaborated to the final products in two additional steps, usually in good yields. The synthetic sequence was amenable to be performed on a preparative scale and 4‐amino benzoxaborole 4b and 6‐hydroxymethyl benzoxaborole 10c have been prepared, without any significant decrease in the overall yield. The amino and hydroxymethyl present at the molecules are useful for further elaboration and/or conjugation to bioactive molecules and therefore we believe that this method should be useful in the development of new compounds for Medicinal Chemistry. The development of a short, simple, and efficient synthesis of amino‐ and hydroxymethyl‐substituted benzoxaboroles is described. The key step was the early stage incorporation of the boron by the borylation of an aniline. The formed boronates were then elaborated to the final products in two additional steps, in good yields.