N-Oxides as Control Element for the Direction of a Sigmatropic Rearrangement: Application as a Switch for Fluorescence

An exceptional level of control over the direction of the (2,3)-sigmatropic rearrangement between N-oxides and alkoxylamine is achieved by simply changing the solvent in which they are dissolved. Protic solvents like water, methanol and hexafluoroisopropanol favour the N-oxide form, while other solvents like acetone, acetonitrile and benzene favour the alkoxylamine. The reaction temperature and nature of the substituents on the alkene affect the rate of rearrangement. A N-oxide fragment was attached to two fluorescent molecules and acted as an on/off switch for their fluorescence. The conversion of alkoxylamines into the corresponding N-oxides has not previously been described and is here termed the 'Reverse Meisenheimer Rearrangement'.