Selectfluor-Mediated Regioselective C-3 Alkoxylation, Amination, Sulfenylation, and Selenylation of Quinoxalin-2(1)-ones.

A Selectfluor-promoted oxidative coupling of quinoxalin-2(1)-ones with alcohols, amines, thiols, and selenols leading to the formation of C-O, C-N, C-S, and C-Se bonds has been developed. The protocol provided good to excellent (53-95%) yields of a wide range of quinoxalin-2(1)-ones decorated with alkoxy, alkylamino, alkylthio, and arylselenyl groups at the C3-position under metal- and photocatalyst-free conditions. The reaction is believed to proceed through a radical pathway. A broad substrate scope including bioactive molecules, mild reaction conditions, readily available coupling partners, high yields, scalability, step-economy, and metal- and photocatalyst-free conditions are the highlighting features of the method. The synthetic utility of the developed protocol was demonstrated by gram-scale synthesis, C3-alkoxylation of quinoxaline-2(1)-one with natural alcohols, and synthesis of aldose reductase (ALR2) inhibitor and histamine-4 receptor antagonist in good yields.