Sulfinic acid azides

Dutt-Wormall reaction. Preparation of dia-zoaminosulfinates by reaction of diazonium salts with aryl- or alkylsulfonamides followed by alkaline hydrolysis to the corresponding sulfinic acid of the sulfonamide and the azide. 

Vinyl sulfones can function as acetylene equivalents through the elimination of sulfinic acid. Reck and coworkers prepared a series of vinyl sulfones for cycloaddition reactions with azides to prepare 1,2,3-triazole derivatives to be incorporated into new oxazolidinone antibacterial agents. Included in the series was the cycloaddition of l-fluoro-l-(phenylsulfonyl)ethylene with the oxizolidinone 156 to give, after elimination of phenylsulfonic acid, a 28% yield of a 1 7 mixture of the regioisomeric 4-and 5-fluorotriazoles (157 and 158) (Fig. 3.91). 

Deprotection of allyl carbonates has been accomplished using a wide variety of nucleophiles (Scheme 9), including formate, sodium borohydride, tri-n-butyl hydride, dimedone, diethylamine, and sodium azide. A recent, noteworthy development is the use of sulfinic acids as nucleophiles in the deprotection of allyl carbonates. Not only were allyl carbonates quantitatively deprotected in 30 min, but the authors also reported the successful deprotection of an allyl ether using catalytic palladium(O). Should this result prove to be general, it would represent in a major development in allyl-based protection of alcohols. 

This action is inhibited by hydrogen cyanide, sodium azide, and carbon monoxide. The inhibition by carbon monoxide is suppressed by light (66). It should be pointed out that cytochrome oxidase, with or without cytochrome c, does not exert any oxidizing action on methionine or cysteine sulfinic acid. 

Arylation of a wide range of NH/OH/SH substrates by oxidative cross-coupling with boronic acids in the presence of catalytic cupric acetate and either triethyl-amine or pyridine at room temperature in air. The reaction works for amides, amines, anilines, azides, hydantoins, hydrazines, imides, imines, nitroso, pyrazi-nones, pyridones, purines, pyrimidines, sulfonamides, sulfinates, sulfoximines, ureas, alcohols, phenols, and thiols. It is also the mildest method for NIO-vinylation. The boronic acids can be replaced with siloxanes or starmanes. The mild condition of this reaction is an advantage over Buchwald-Hartwig s Pd-catalyzed cross-coupling. The Chan-Lam C-X bond cross-coupling reaction is complementary to Suzuki-Miyaura s C-C bond cross-coupling reaction. 

Uozumi and coworkers prepared phosphine/palladium complexes supported on polyethylene glycol-polystyrene graft polymer. - This amphiphilic resin-supported palladium complex eftidently catalyzed the alkylation of allylic acetates in water with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodium azide, sodium sulfinate, phenylboronic acid, and sodium tetraphenylborate to give the corresponding allylic-substituted products in quantitative yields. 

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