Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan.
Chem Commun (Camb). 2010 Jan 28;46(4):511-21. doi: 10.1039/b922033j. Epub 2009 Nov 27.
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.
总结了 N-三氟甲亚氨基-λ(3)-溴代烷的合成和反应。高价亚氨基溴代烷在过渡金属自由条件下在环境温度下作为一种非常活跃的氮烯物种起作用，这可能是因为与芳基-λ(3)-碘代烷相比，芳基-λ(3)-溴代烷基团的超亲核性增加。亚氨基-λ(3)-溴代烷对烯烃进行立体特异性氮丙啶化和向芳族氮杂环、三烷基胺和碘代苯的转烷基化反应。还讨论了二氟-λ(3)-溴代烷诱导的伯芳基磺酰胺的Hofmann 重排反应。
