Nucleophiles sulfone-containing

Guzman-Martinez and Hoveyda introduced bidentate sulfonate-containing NHC-copper(I) complexes L19 and L20 (Scheme 24) for allylic displacements with boron nucleophiles followed by subsequent oxidation to the correspraiding... 

The 1,2-addition of sulfone-containing nucleophiles to aldehydes is a highly valuable tool in synthetic chemistry. H owever, since the first addition of a-chlorophenyl-sulfone to aromatic aldehydes under PTC in 1998 [65], only one further approach has been reported. Hu et al. reported the enantioselective 1,2-addition of Me3SiCp2 S02Ph and PhS02Cp2H to aromatic aldehydes catalyzed by a chiral aUcaloid-based quaternary ammonium salt (Scheme 29.30) [66], Several chiral ammonium salts were screened and the best results were obtained with cinchonine and quinine... 

Fiber-Reactive Dyes. These dyes can enter iato chemical reaction with the fiber and form a covalent bond to become an iategral part of the fiber polymer. They therefore have exceptional wetfastness. Thein main use is on ceUulosic fibers where they are appHed neutral and then chemical reaction is initiated by the addition of alkaH. Reaction with the ceUulose can be by either nucleophilic substitution, using, for example, dyes containing activated halogen substituents, or by addition to the double bond in, for example, vinyl sulfone, —S02CH=CH2, groups. 

Sulfonic esters are most frequently prepared by treatment of the corresponding halides with alcohols in the presence of a base. The method is much used for the conversion of alcohols to tosylates, brosylates, and similar sulfonic esters. Both R and R may be alkyl or aryl. The base is often pyridine, which functions as a nucleophilic catalyst, as in the similar alcoholysis of carboxylic acyl halides (10-21). Primary alcohols react the most rapidly, and it is often possible to sulfonate selectively a primary OH group in a molecule that also contains secondary or tertiary OH groups. The reaction with sulfonamides has been much less frequently used and is limited to N,N-disubstituted sulfonamides that is, R" may not be hydrogen. However, within these limits it is a useful reaction. The nucleophile in this case is actually R 0 . However, R" may be hydrogen (as well as alkyl) if the nucleophile is a phenol, so that the product is RS020Ar. Acidic catalysts are used in this case. Sulfonic acids have been converted directly to sulfonates by treatment with triethyl or trimethyl orthoformate HC(OR)3, without catalyst or solvent and with a trialkyl phosphite P(OR)3. ... 

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... 

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