Negative ion Wolff rearrangement of some diazoketones: A theoretical mechanistic study

The mechanism of the Wolff rearrangement of some deprotonated diazocarbonyl compounds has been studied using density functional calculations, for both the gas and aqueous phases. The anionic rearrangement of the deprotonated analogues proceeds in a similar manner to the neutral counterparts. In the gas phase, the syn and anti conformers form the deprotonated ketene product concertedly. In certain analogues, the reaction of the anti conformer occurs non-concertedly, involving a deprotonated carbenelike intermediate. The migratory aptitude is similar to that in the neutral rearrangement, except that methoxy and amino substituents exchange positions. (C) 2017 Elsevier B.V. All rights reserved.