Dess-Martin Peridoninane (DMP)and IBX have been used extensively since their development for the oxidation of organic substrates, particularly alcohols. We were able to demonstrate that DMP carries out oxidative dearomatisation on electron rich pyrroles1 via novel mechanism2 to provide products of high value as synthetic intermediates for natural product synthesis.3 The scope of this reaction was limited as electron deficient pyrroles were unreactive. We have identified how to activate DMP and analogues of IBX to increase their reactivity towards heterocycles and arenes.