Rearrangement benzenesulfonyl azide

The mixture 258 was converted to the unstable benzenesulfonyl aziridine 259 by treatment with an excess of benzenesulfonyl azide in benzene. Ace-tolysis of 259 with acetic acid and sodium acetate at room temperature for several days afforded the crystalline mixture of diastereoisomers represented by the formula 260. The aziridine rearrangement was regiospecific and 260 was the only product detected during this rearrangement. Lithium aluminium hydride reduction of 260 followed by acetylation yielded the mixture 261 in 85% yield. Selective hydrolysis of 261 afforded 262 in quantitative yield. The diastereoisomeric mixture 262 was converted into the diols 263 by hydrogenolysis. The diol mixture was oxidized with chromium trioxide... 

The reaction of cyclic 1,1-enediamines 7 and 8 with azides appears interesting. Nitro-substituted 1,1-enediamines 7 reacted with benzenesulfonyl azide to give triazoles 225 in moderate yields. Other secondary 1,1-enediamines analogues gave similar products in comparable yields. The reaction has been postulated to proceed by a sequence of 1,3-cycloaddition to 223, a Dimroth rearrangement to 224 and deamination to 225 (Scheme 12)174. Junjappa and coworkers175 have reported that 1,1-enediamines... 

The thermal decomposition of sulfonyl azides, like azido formates, appears to involve nitrene intermediates . The thermolysis of benzenesulfonyl azide is first order and the rate coefficient is relatively insensitive to solvent changes or substituent effects . o-Nitrobenzenesulfonyl azide decomposes with evolution of nitric oxide and nitrogen the rate of azide disappearance however, is about the same as that for other benzenesulfonyl azides and it appears that the reaction leading to NO can be explained by an intramolecular rearrangement in the nitrene intermediate. This is in contrast to the decomposition of o-nitrophenyl azide (vide infra) where rearrangement occurs in the transition state of the rate-determining step. 

Fascinating rearrangements of aziridines have been applied to the synthesis of diterpene alkaloids by Wiesner and co-workers (Scheme 40). For example, the ester 217, prepared from cyclopentadiene carboxylate (215) and the benzyne precursor 216 by a Diels-Alder reaction, was converted to the aziridine 218 by treatment with benzenesulfonyl azide in 83% yield. When the aziridine 218 was heated with water for 24 h, the hydroxy ester 219 was obtained in 97% yield subsequent oxidation with the Jones reagent afforded the ketone 220. This rearrangement is analogous to that of the benzenesulfonylaziridine of norbomene. ... 

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