Hypervalent N-sulfonylimino-lambda(3)-bromane: active nitrenoid species at ambient temperature under metal-free conditions.
The synthesis and reactions of N-triflylimino-lambda(3)-bromane are summarized. The hypervalent iminobromane functions as a highly active nitrenoid species at ambient temperature under transition metal-free conditions, probably because of the increased hypernucleofugality of aryl-lambda(3)-bromanyl groups compared to that of aryl-lambda(3)-iodanyl groups. The imino-lambda(3)-bromane undergoes stereospecific aziridination of olefins and transylidation to aromatic nitrogen heterocycles, trialkylamines and iodobenzenes. Difluoro-lambda(3)-bromane-induced Hofmann rearrangement of primary arylsulfonamides is also discussed.
Ochiai
Masahito
M
Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan. mochiai@ph.tokushima-u.ac.jp
Miyamoto
Kazunori
K
Hayashi
Satoko
S
Nakanishi
Waro
W
D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D013450:Sulfones / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
D007097:Imines; D013450:Sulfones; C540083:sulfonylimino-lambda3-bromane