American Chemical Society
ol1c02539_si_001.pdf (4.78 MB)

Switchable Oxidative Reactions of N‑allyl-2-Aminophenols: Palladium-Catalyzed Alkoxyacyloxylation vs an Intramolecular Diels–Alder Reaction

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journal contribution
posted on 2021-09-27, 19:05 authored by Sabrina Giofrè, Manfred Keller, Leonardo Lo Presti, Egle M. Beccalli, Letizia Molteni
The Pd­(II)-catalyzed reaction of N-allyl-2-aminophenols in the presence of PhI­(OCOR)2 as the oxidant resulted in an alkoxyacyloxylation process, with the formation of functionalized dihydro-1,4-benzoxazines. The reaction performed in the absence of palladium catalyst switched to an intramolecular Diels–Alder reaction (IMDA) pathway, which was the result of an oxidative dearomatization of the 2-aminophenol, nucleophilic addition, and Diels–Alder reaction cascade, highlighting the role of the oxidant as both a nucleophilic donor and an oxidizing agent.