Silver‐Induced Cα(sp3)–H Activation of Benzylamines Followed by [1,5]‐ versus [1,3]‐Rearrangement: A Strategy towards the Regioselective Synthesis of Spiro‐Dihydropyrroles

Abstract

For the first time in pyrrole chemistry, silver‐mediated Cα(sp3)–H bond activation of benzylamines followed by [1,5]‐ versus [1,3]‐rearrangement towards the regioselective synthesis of spiro‐dihydropyrrole derivatives has been achieved. The reaction proceeds through cleavage of the benzylamine C–N bond promoted by the crucial silver carbonate followed by a regioselective [1,5]‐rearrangement with dialkyl but‐2‐ynedioate in the presence of isatin or N‐methylisatin. Equally, N‐substituted isatin with benzyl, allyl, ethyl, propyl, and n‐butyl substituents proceeds through an alternate [1,3]‐rearrangement strategy. The study highlights the recycling of silver species and for selective use in oxidative C–N and C–C coupling reactions.