The solution-phase synthesis of a library of 2-Aminobenzimidazole is described, In this approach, an array of 2-alkoxybenzimidazoles was synthesized using coupling reaction between varipus chloroformates and azidoanilines, N-alkylation and cyclization voa Staudinger reaction followed by aza-Wittig reaction. These substrates were finally treated with under smart diversity-building cleavage conditions using a series of aluminum amide complexes to afford the corresponding 2-Aminobenzoxazole products in excellent yields and purity.