Bagi, Amin Hossein Khaledi, Yousef Ghari, Hossein Arndt, Sebastian Stephen K. Hashmi, A. Yates, Brian F. Ariafard, Alireza A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C–C Multiple Bonds 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 <i>syn</i>-addition and outer-sphere <i>anti</i>-addition (Friedel–Crafts-type mechanism). In this article, the AuCl<sub>3</sub>-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. alcohol substrates;CEIS;theory calculations;outer-sphere mechanism;future studies;protonated substrate;functionalization;Mechanistic Investigation;furan auration acts;AuCl 3;novel mechanism;vinyl ketone;allenyl ketone;inner-sphere syn;bond 2016-10-17
    https://acs.figshare.com/articles/journal_contribution/A_Mechanistic_Investigation_of_the_Gold_III_-Catalyzed_Hydrofurylation_of_C_C_Multiple_Bonds/4126791
10.1021/jacs.6b05742.s001