2,2-Dimethyl-2-( o-nitrophenyl)acetyl group (DMNA) was explored as an assisted cleavage protecting group for amines and a one-step deprotection condition was developed for its efficient removal using hydrogenation in the presence of Pd–C or PtO 2 catalyst and 10% HOAc in MeOH. DMNA was found to be especially useful for the synthesis of gem-diamino compounds using Hofmann rearrangement.