Gas‐phase synthesis of hydrodiphenylcyclopropenylium via nonclassical Favorskii rearrangement from alkali‐cationized α,α′‐dibromodibenzyl ketone

The gas‐phase synthesis of hydrodiphenylcyclopropenylium from alkali‐cationized α,α′‐dibromodibenzyl ketone (1) via nonclassical Lewis‐acid‐induced Favorskii rearrangement has been studied by electrospray ionization/tandem mass spectrometry (ESI‐MS/MS) and theoretical methods, showing that cations [1–Br] + by debromination from 1 and 1 · M + (M = Li or Na) by alkali‐metal cationization of 1 could convert into the protonated diphenylcyclopropenone 2 · H + by collision‐induced dissociation in the gas phase. A concerted mechanism for the Lewis‐acid‐induced Favorskii rearrangement from alkali‐metal‐cationized α,α′‐dibromodibenzyl ketone was proposed and studied, based on mass spectrometric results and theoretical methods. Copyright © 2010 John Wiley & Sons, Ltd.