Categories: N-S Bond Formation >
Synthesis of Sulfonimidamides
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Recent Literature
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.
Following 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.
Reactions of sulfonimidoyl fluorides with anilines and Ca(NTf2)2 proceed with
inversion of the stereocenter at the sulfur atom. Full enantiospecificity was
observed for most studied non-heterocyclic anilines. A chelate-type coordination
of the sulfonimidoyl group to Ca(NTf2)2 and the formation of a SN2-like transition state is proposed, in which leaving F- coordinates with
the Ca2+ ion.
D.-D. Liang, N. Lional, B. Scheepmaker, M. Subramaniam, G. Li, F. M. Miloserdov,
H. Zuilhof, Org. Lett., 2023, 25,
5666-5670.