Abstract
There have been several studies on the solvolysis mechanisms for alkanesulfonyl chlorides (RSO2Cl) and arenesulfonyl chlorides (ArSO2Cl). The earlier of these studies were reviewed a little over thirty years ago by Gordon, Maskill and Ruasse (Chem. Soc. Rev. 1989, 18, 123–151) in a contribution entitled “Sulfonyl Transfer Reactions”. The present review will emphasize more recent contributions and, in particular, the application of the extended Grunwald–Winstein equation and kinetic solvent isotope effects to the solvolysis reactions. There is also an appreciable number of reports concerning the corresponding anhydrides with the chloride leaving group replaced by the appropriate sulfonate leaving group, concerning sulfamoyl chlorides (ZZ'NSO2Cl) with Z and Z' being alkyl or aryl and concerning the solvolysis of chlorosulfate esters (alkoxy- or aryloxysulfonyl chlorides), with the structures ROSO2Cl or ArOSO2Cl. The solvolyses of these additional types of sulfur(VI) substrates will be the topics of a future review.
Highlights
Introduction to solvolyses of sulfonyl halidesIn medicinal chemistry, sulfonyl chlorides are good building blocks to intermediates and complex scaffolds of sulfonamides
Maskill and co-workers [26,27] investigated the solvolyses of 2,4dimethoxybenzenesulfonyl chloride and of the 2,4,6-trimethylbenzenesulfonyl chloride in 50% TFE/50% water (50% TFE) and in the highly ionizing 97% TFE
For a rigid explanation of how the substitution reactions of sulfonyl chlorides proceed during solvolysis, a detailed picture of the influence of the solvent as one proceeds from reactants to products, such as one developed based on the procedures outlined above [31] would be required
Summary
Sulfonyl chlorides are good building blocks to intermediates and complex scaffolds of sulfonamides. The only small difference between the specific rates of reaction with solvent water and the overall value with added hydroxide ion suggested [14], but does not demand, a unimolecular SN1 pathway [28]. Overall, it was concluded [28] that the hydrolyses of both the methane- and benzenesulfonyl chlorides usually involve an SN2 pathway. The ∆Cp# values correlated very well against ∆S# values, except for an unusually low value for the p-MeO
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