Metal-Free Synthesis\nof Polysubstituted Triazoloquinoxalines\nUsing Alkynols as the Key Building Blocks

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