Synthesis of Sulfonimidamides

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A one-pot approach to both sulfoximines and sulfonimidamides exploits the high electrophilicity of sulfinyl nitrenes. These rare reactive intermediates are generated from a sulfinylhydroxylamine (R-O-N=S=O) reagent through an N-O bond fragmentation process. Addition of carbon and nitrogen nucleophiles enables the synthesis of sulfoximines and sulfonimidamides in just 15 min.
T. Q. Davis, M. J. Tilby, J. Ren, N. A. Parker, D. Skolc, A. Hall, F. Duarte, M. C. Willis, J. Am. Chem. Soc., 2020, 142, 15445-15453.

NH-Sulfonimidamides are prepared in good yields by a ligand-free copper-catalyzed coupling of primary sulfinamides with secondary amines in the presence of air as the terminal oxidant. The reaction occurs at room temperature and shows good functional group tolerance. A sulfanenitrile is proposed as an intermediate in this oxidative amination.
P. Wu, J. Demaerel, D. Kong, D. Ma, C. Bolm, Org. Lett., 2022, 24, 6988-6992.

A redox-neutral Ni(II)-catalyzed addition of (hetero)aryl boroxines to N-sulfinyltritylamine (TrNSO). The initially formed sulfinamides undergo oxidative chlorination with trichloroisocyanuric acid to produce sulfonimidoyl chlorides as key intermediates. Whereas in situ reaction with amines delivers sulfonimidamides, hydrolysis provides primary sulfonamides.
P. K. T. Lo, M. C. Willis, J. Am. Chem. Soc., 2021, 143, 15576-15581.

The reaction of a N-silyl sulfinylamine reagent with Grignard, organolithium, or organozinc reagents provides a broad range of (hetero)aryl, alkenyl, and alkyl primary sulfinamides. Treatment of these primary sulfinamides with an amine in the presence of a hypervalent iodine reagent leads directly to sulfonimidamides.
M. Ding, Z.-X. Zhang, T. Q. Davies, M. C. Willis, Org. Lett., 2022, 24, 1711-1715.

A one-pot, two-step mechanochemical synthesis of sulfonimidamides requires neither a solvent nor inert conditions. In a mixer mill, sulfinamides are rapidly converted to sulfonimidoyl chlorides by oxidative chlorination with N-chlorosuccinimide (NCS). Subsequent substitutions with amines provides a wide range of diversely substituted sulfonimidamides.
S. Terhorst, T. Jansen, T. Langletz, C. Bolm, Org. Lett., 2022, 24, 4109-4113.