Efficient Synthesis of Unsymmetrical Sulfamides via a Lossen‐Like Rearrangement

Abstract

A convenient one‐pot synthesis of unsymmetrical sulfamides via a Lossen‐like rearrangement is reported. The protocol operates under simple conditions at room temperature and does not require an inert atmosphere and a dry solvent. The ability of N‐hydroxy arenesulfonamide O‐derivatives to generate under mild conditions N‐sulfonylimine intermediates was a trigger point for developing a general synthetic strategy towards unsymmetrical sulfamides. The synthetic potential of the methodology has been investigated by preparing cyclic sulfamides and new potential chiral organocatalysts.magnified image

Chan–Lam coupling reaction of sulfamoyl azides with arylboronic acids for synthesis of unsymmetrical N-arylsulfamides

“…A Lossen-like rearrangement was demonstrated and this reaction carried out at room temperature, however, over 12 h were required to synthesize the sulfamides (Scheme 1, route C). 5 Therefore, it is still necessary to develop a more efficient and less stringent method to obtain the desired product.…”

Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces

“…The disulfide 1 was synthesized following our previous procedure from commercially available 4-aminophenyl disulfide and the readily prepared 4-methyl- N -(tosyloxy)benzenesulfonamide in the presence of triethylamine ( Scheme 2 ) [ 38 ]. The desired product sulfamide 1 was obtained in 60% yield after purification on silica gel and was fully characterized before the preparation of sulfamide-terminated SAMs ( Supporting Information File 1 ).…”

“…Besides applications in medicinal chemistry, sulfamide groups have been incorporated in self-assembling molecules [22–27], peptides [28], polymers [29], ligands [30], chiral auxiliaries [31–33] and in organocatalysts [34–37]. In light of the importance of the sulfamide functionality, our group has recently reported a straightforward preparation of unsymmetrical sulfamides from commercially available amines and N -hydroxyarenesulfonamide O -derivatives under simple conditions [38–39]. The method works at room temperature without needing inert atmosphere or dry solvent.…”

Stereoselective Multibond-Forming Process towards Functionalized Sulfamide-Containing Polycycles

“…Bicyclic sulfamides 1 were synthesized according to our previously reported protocols. 11 NMR data were recorded at 300 MHz (Bruker Avance spectrometer) in CDCl 3 using the residual CHCl 3 signal as reference for 1 H NMR (δ = 7.27) and the deuterated solvent signal as reference for 13 C NMR (δ = 77.16) spectra. Coupling constants (J) are given in hertz (Hz) and standard abbreviations are used to describe the signal multiplicities.…”

“…10 We have recently developed a straightfor-ward strategy for the formation of unsymmetrical sulfamides starting from commercially available amines and easily accessible N-hydroxy arenesulfonamide O-derivatives. 11 This methodology has also been used for the preparation of cyclic sulfamides.…”