Difluoro-λ3-bromane-induced hofmann rearrangement of sulfonamides: Synthesis of sulfamoyl fluorides

Masahito Ochiai, Takuya Okada, Norihiro Tada, Akira Yoshimura, Kazunori Miyamoto, Motoo Shiro

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

(Chemical Equation Presented) We report the first example of Hofmann rearrangement of primary arenesulfonamides, which relies on the use of p-trifluoromethylphenyl(difluoro)-λ3-bromane and affords N-arylsulfamoyl fluorides selectively at room temperature. Reaction of aryl-λ3-iodanes with p-toluenesulfonamide affords sulfonylimono-λ3-iodanes, being excellent progenitors for generation of metal-nitrenoid species. In marked contrast, reaction of the difluoro-λ3-bromane with p-toluenesulfonamide in benzene produced unique N-p-tolylsulfamoyl fluoride in a high yield, through Hofmann rearrangement. Arenesulfonamides with electron-donating (p-MeO and o-Me) and -withdrawing substituents (p-F, p-Cl, and p-CF3) efficiently undergoes the λ3-bromane-induced Hofmann rearrangement. The structure of N-p-tolylsulfamoyl fluoride was determined by a single-crystal X-ray analysis. The differences in nucleofugality between aryl- λ3-iodanyl and aryl-λ3-bromanyl groups, the later being greater, probably play a pivotal role in determining the reaction course. The results obtained from the reaction of 2,3,5,6- tetramethylbenzenesulfonamide strongly suggest that generation of sulfonyl nitrene will not be involved in this rearrangement.

Original languageEnglish
Pages (from-to)8392-8393
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number24
DOIs
Publication statusPublished - 24 Jun 2009
Externally publishedYes

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Sulfonamides
X ray analysis
Fluorides
Benzene
Single crystals
Electrons
Metals
Temperature
X-Rays

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Difluoro-λ3-bromane-induced hofmann rearrangement of sulfonamides : Synthesis of sulfamoyl fluorides. / Ochiai, Masahito; Okada, Takuya; Tada, Norihiro; Yoshimura, Akira; Miyamoto, Kazunori; Shiro, Motoo.

In: Journal of the American Chemical Society, Vol. 131, No. 24, 24.06.2009, p. 8392-8393.

Research output: Contribution to journalArticle

Ochiai, Masahito ; Okada, Takuya ; Tada, Norihiro ; Yoshimura, Akira ; Miyamoto, Kazunori ; Shiro, Motoo. / Difluoro-λ3-bromane-induced hofmann rearrangement of sulfonamides : Synthesis of sulfamoyl fluorides. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 24. pp. 8392-8393.
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abstract = "(Chemical Equation Presented) We report the first example of Hofmann rearrangement of primary arenesulfonamides, which relies on the use of p-trifluoromethylphenyl(difluoro)-λ3-bromane and affords N-arylsulfamoyl fluorides selectively at room temperature. Reaction of aryl-λ3-iodanes with p-toluenesulfonamide affords sulfonylimono-λ3-iodanes, being excellent progenitors for generation of metal-nitrenoid species. In marked contrast, reaction of the difluoro-λ3-bromane with p-toluenesulfonamide in benzene produced unique N-p-tolylsulfamoyl fluoride in a high yield, through Hofmann rearrangement. Arenesulfonamides with electron-donating (p-MeO and o-Me) and -withdrawing substituents (p-F, p-Cl, and p-CF3) efficiently undergoes the λ3-bromane-induced Hofmann rearrangement. The structure of N-p-tolylsulfamoyl fluoride was determined by a single-crystal X-ray analysis. The differences in nucleofugality between aryl- λ3-iodanyl and aryl-λ3-bromanyl groups, the later being greater, probably play a pivotal role in determining the reaction course. The results obtained from the reaction of 2,3,5,6- tetramethylbenzenesulfonamide strongly suggest that generation of sulfonyl nitrene will not be involved in this rearrangement.",
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