Sulfene mechanism in the pyridine-catalysed reactions of alkanesulfonyl halides with phenols

The quest for sulfoquinone imine intermediates in the reaction of sulfanilic acid derivatives with nucleophiles

“…It is interesting to note, however, that, on going from the highly polar aqueous acetonitrile to the less polar acetonitrile, selectivity increases considerably. This observation is in line with the results of Skripnik et al, 8 who found that in the pyridine-catalysed phenolysis of phenylmethanesulfonyl chloride in organic solvents spanning a broad range of medium polarity, although both the elimination-addition and the addition-elimination mechanisms are followed competitively, the contribution of the former increases sharply as solvent polarity increases.…”

A New Route to Sulfonamides via Intermolecular Radical Addition to Pentafluorophenyl Vinylsulfonate and Subsequent Aminolysis

“…This sulfene mechanism has been shown by King et al to be the predominant mechanistic pathway for the hydrolysis of sulfonyl halides at high pH. 8 Lyashchuk et al have also demonstrated that the sulfene mechanism operates in the pyridine-catalyzed reaction of alkanesulfonyl chlorides with phenols, 9 adding further support for our proposed mechanism.…”

Experimental and Theoretical Insights into the Mechanisms of Sulfate and Sulfamate Ester Hydrolysis and the End Products of Type I Sulfatase Inactivation by Aryl Sulfamates

“…Extending the trend observed on going from X = O to X = NR, the sulfonate 10 (X = CH 2 ) is computed to dissociate to phenoxide plus sulfene (SO 2 CH 2 ) with an energy of only 5.7 kcal/mol (Table ). Experimentally, SO 2 CH 2 has been generated from methanesulfonyl chloride by treatment with base . The reaction of p -nitrophenyl methanesulfonate with OH – is believed to occur by an addition–elimination mechanism, rather than through the intermediacy of sulfene, presumably because the high p K a value of the ester prevents the deprotonation step of the E1cb pathway in aqueous solution .…”