Benchtop-Stable Hypervalent Bromine(Iii) Compounds: Versatile Strategy And Platform For Air- And Moisture-Stable Lambda(3)-Bromanes

We present the first synthesis of air/moisture-stable.3-bromanes (9 and 10) by using a cyclic 1,2-benzbromoxol-3-one (BBX) strategy. X-ray crystallography and NMR and IR spectroscopy of N-triflylimino-lambda(3)-bromane (12) revealed that the bromine(III) center is effectively stabilized by intramolecular R-Br-O hypervalent bonding. This strategy enables the synthesis of a variety of air-, moisture-, and benchtop-stable Br-hydroxy, -acetoxy, -alkynyl, -aryl, and bis[(trifluoromethyl)sulfonyl]methylide lambda(3)-bromane derivatives.