Sulfonyl sulfur, nucleophilic

The order of nucleophilicity toward a sulfonyl sulfur has been reported as... 

As an alternative, Harpp and coworkers reacted benzenesulfinyl chloride with the trimethylsilyl derivative of menthol to form the diastereomeric esters in 91% yield the epimer of configuration R could be isolated by crystallization in unspecified yield. Grossert and coworkers prepared ester 19 in 51% yield as a mixture of diastereomers by treating p-toluenesulfonyl chloride with sodium p-toluenesulfinate in DMF containing menthol. It was postulated that initial nucleophilic attack by the sulfinate oxygen on the sulfonyl sulfur atom gave the mixed sulfonate-sulfinate anhydride 21, which then reacted... 

Reactivity toward nucleophiles and comparison with other electrophilic centers 152 Paths for nucleophilic substitution of sulfonyl derivatives 156 Direct substitution at sulfonyl sulfur stereochemistry 157 Direct substitution at sulfonyl sulfur stepwise or concerted 158 The elimination-addition path for substitution of alkanesulfonyl derivatives 166 Homolytic decomposition of a-disulfones 172 10 Concluding remarks 173 Acknowledgement 174 References 174... 

Earlier (Table 6, p. 119) we saw data on the reactivity of various nucleophiles toward an aryl sulfinyl sulfone in (139), a substitution that also involves an arenesulfinate as the leaving group, but one in which the substitution takes place at a sulfinyl ( S=0) rather than a sulfenyl ( S) sulfur. In Section 9 we present data on the rates of reaction of the same nucleophiles in an analogous substitution at a sulfonyl sulfur, Nu- + PhS02S02Ph - PhS02Nu + PhS02. At that point we will discuss how changing the oxidation state of the sulfur atom at which the substitution occurs... 

Rogne (1970) has measured the reactivity of some of the same nucleophiles toward benzenesulfonyl chloride in water at 25°. When log km for reaction of these nucleophiles with PhSOjCl is plotted vs. the log values for the same nucleophiles from Table 10, one obtains a good straight line relationship with a slope of about 0.8. This shows that the reactivity pattern observed with PhSOjSOjPh and shown in Table 10 is representative of what will be observed generally in nucleophilic substitution at the sulfonyl sulfur of reactive sulfonyl substrates. 

The reactions represented by (191) are all nucleophilic substitutions occurring at a sulfonyl sulfur. Besides cpdisulfones substitutions of this kind are also of frequent occurrence in the chemistry of many other types of sulfonyl derivatives such as sulfonyl halides, aryl esters of sulfonic acids, etc., and many of the general aspects of their behaviour and mechanism have been examined in considerable detail. Most of the remainder of this section will be devoted to consideration of the results of such studies. 

The order of nucleophilicity toward a sulfonyl sulfur has been reported as OH > RNH2 > N3 > F > AcO" > Cl > H20 > I. 1732 This order is similar to that at a carbonyl carbon (p. 351). Both of these substrates can be regarded as relatively hard acids, compared to a saturated carbon which is considerably softer and which has a different order of nucleophilicity (p. 350). 

With the exception of F , the relative reactivities of nucleophiles toward sulfonyl sulfur are very similar to their relative reactivities in the same solvent toward carbonyl carbon. J. L. Kice and E. Legan, J. Amer. Chem. Soc., 95, 3912 (1974). 

Sulfonamides are hydrolyzed more slowly than amides of carboxylic acids examination of the structures involved shows us what probably underlies this difference. Nucleophilic attack on a trigonal acyl carbon (Sec. 20.4) is relatively unhindered it involves the temporary attachment of a fourth group, the nucleophilic reagent. Nucleophilic attack on tetrahedral sulfonyl sulfur is relatively hindered it involves the temporary attachment of a /// group. The tetrahedral... 

Nucleophilic substitution reactions of anilines at a sulfonyl sulfur (tetra-coordinated sulfur) atom have been widely studied. Some of the works are presented in Table 9. 

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