Hossein Bagi, AminKhaledi, YousefGhari, HosseinArndt, SebastianHashmi, A. Stephen K.Yates, Brian F.Ariafard, Alireza2025-06-242025-06-240002-7863ORCID:/0000-0003-2383-6380/work/163628653http://www.scopus.com/inward/record.url?scp=84994493013&partnerID=8YFLogxKhttps://hdl.handle.net/1885/733764847The gold-catalyzed direct functionalization of aromatic C-H bonds has attracted interest for constructing organic compounds which have application in pharmaceuticals, agrochemicals, and other important fields. In the literature, two major mechanisms have been proposed for these catalytic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanism). In this article, the AuCl3-catalyzed hydrofurylation of allenyl ketone, vinyl ketone, ketone, and alcohol substrates is investigated with the aid of density functional theory calculations, and it is found that the corresponding functionalizations are best rationalized in terms of a novel mechanism called "concerted electrophilic ipso-substitution" (CEIS) in which the gold(III)-furyl σ-bond produced by furan auration acts as a nucleophile and attacks the protonated substrate via an outer-sphere mechanism. This unprecedented mechanism needs to be considered as an alternative plausible pathway for gold(III)-catalyzed arene functionalization reactions in future studies.The authors gratefully acknowledge the generous allocation of computing time from the Australian National Computational Infrastructure and the University of Tasmania. A.H.B., Y.K., H.G., and A.A. appreciate financial support from the Iran Science Elites Federation.10enPublisher Copyright: © 2016 American Chemical Society.2016-11-0910.1021/jacs.6b0574284994493013