Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides

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.

Keywords: Grunwald–Winstein equation; Hammett equation; correlation; mechanism; solvolysis; sulfonyl halides.