Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry,a nd provide attractive bioisosteres for sulfonamides.However,there remain few operationally simple methods for their preparation. Here,t he synthesis of NH-sulfonimidamides is achieved directly from sulfenamides,themselves readily formed in one step from amines and disulfides.Ahighly chemoselective and one-pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source,and in the presence of 1equivalent of acetic acid. Awide range of functional groups are tolerated under the developed reaction conditions,w hich also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel SNsulfanenitrile species as intermediates.Several alkoxy-amino-l 6 -sulfanenitriles are prepared with different alcohols,a nd shown to be alkylating agents to arange of nucleophiles. Scheme 1. Potential bioisosteres for sulfones and sulfonamides, examples of bioactive sulfonimidamides, and current strategies for the synthesis of sulfonimidamides.