Linked Life Data

19485369

Source:http://linkedlifedata.com/resource/pubmed/id/19485369

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
24
pubmed:dateCreated
2009-6-17
pubmed:abstractText
We report the first example of Hofmann rearrangement of primary arenesulfonamides, which relies on the use of p-trifluoromethylphenyl(difluoro)-lambda(3)-bromane and affords N-arylsulfamoyl fluorides selectively at room temperature. Reaction of aryl-lambda(3)-iodanes with p-toluenesulfonamide affords sulfonylimono-lambda(3)-iodanes, being excellent progenitors for generation of metal-nitrenoid species. In marked contrast, reaction of the difluoro-lambda(3)-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-CF(3)) efficiently undergoes the lambda(3)-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-lambda(3)-iodanyl and aryl-lambda(3)-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.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jun
pubmed:issn
1520-5126
pubmed:author
pubmed:issnType
Electronic
pubmed:day
24
pubmed:volume
131
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
8392-3
pubmed:meshHeading
pubmed:year
2009
pubmed:articleTitle
Difluoro-lambda3-bromane-induced Hofmann rearrangement of sulfonamides: synthesis of sulfamoyl fluorides.
pubmed:affiliation
Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan. mochiai@ph.tokushima-u.ac.jp
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't