Cyclic saturated aminosulfonyl fluorides were synthesized as their HCl salts. The compounds were found to be stable upon storage and could be used for the protecting-group-free synthesis of sulfonamides. In the presence of the -SO F group, the nitrogen atom could be modified by means of acylation, arylation, or reductive amination to give products that have high potential for the synthesis of bioactive compounds.
Saturated bicyclic sultams represent a promising class of sp 3-rich three-dimensional scaffolds of outmost importance to organic and medicinal chemistry. In this review with 99 references, synthesis, properties, and applications of these compounds are surveyed. The literature data are categorized according to the structural types (i.e. fused, bridged, and spirocyclic compounds), as well as homologous series
Structural
restriction of the sulfonamide bond was used to design
sultams with abnormal geometric parameters. Based on analysis of tertiary
aliphatic sulfonamides published in the Cambridge crystallographic
database, Paquette’s sultams (i.e., bridged bicyclic sultams
with a bridgehead nitrogen atom) were outlined, and a number of these
compounds (including the novel smallest representative, 2-thia-1-azabicyclo[2.1.1]hexane
2,2-dioxide) were synthesized by cyclization of the corresponding
amino sulfonyl fluorides. A series of tertiary aliphatic sulfonamides
was studied by crystallographic and quantum chemical methods. It was
found that the s-character of the nitrogen lone pair is the most important
factor defining properties of the S–N bond. Thus, going from
the sp3-hybrid lone pair in common sulfonamides to the
sp-like lone pair in the smallest Paquette’s sultam resulted
in an increase in S–N bond length by ca. 0.06 Å. The strain
energy of ca. 30 kcal/mol was predicted for the latter compound, which
was higher than for any existing sulfonamides studied.
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