Metal-Free Synthesis of Polysubstituted Triazoloquinoxalines Using Alkynols as the Key Building Blocks.

o -Phenylenediamines, o -nitroanilines, and Boc- o -phenylenediamines were converted to N -Ts/Ns- o -phenylenediamines, followed by Mitsunobu alkylation with prop-2-yn-1-ols. After one-pot azidation, the resulting intermediates underwent Huisgen cycloaddition, which yielded Ts/Ns-dihydrotriazoloquinoxalines. Cleavage of the arylsulfonyl moiety provided (dihydro)triazoloquinoxalines with the possibility of modifying the N 5 position. The application of but-3-yn-1-ols and pent-4-yn-1-ols allowed the preparation of benzotriazolodiazepines and benzotriazolodiazocines. The developed protocols enable the preparation of diversely substituted products from readily available starting materials under mild and metal-free conditions.