A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C–C Multiple Bonds

• Published in: Journal of the American Chemical Society 2016-11, Vol.138 (44), p.14599-14608
• Main Authors: Hossein Bagi, Amin, Khaledi, Yousef, Ghari, Hossein, Arndt, Sebastian, Hashmi, A. Stephen K, Yates, Brian F, Ariafard, Alireza
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b05742

The 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.