Intermolecular electrophilic O-amination of alcohols

We report the first examples of an intermolecular electrophilic O-amination of aliphatic alcohols. Thus, the new reagents, fluorenone oxime tosylate, 5a, or mesylate, 5b, permit O-amination of diverse alcohols in the presence of NaH under mild conditions. By following the formation of the resulting oxime ethers, 6, the reaction was shown to be sensitive to steric effects in the alcohol. Furthermore, the presence of an aromatic ring or of a double bond in the alcohol molecule (benzyl, allyl) was found to increase the reaction rate.