title: A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C-C Multiple Bonds.
abstract: 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.
authors.affiliation: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University , Shahrak Gharb, Tehran 1467686831, Iran.
authors.forename: Amin
authors.initials: A
authors.lastname: Hossein Bagi
authors.affiliation: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University , Shahrak Gharb, Tehran 1467686831, Iran.
authors.forename: Yousef
authors.initials: Y
authors.lastname: Khaledi
authors.affiliation: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University , Shahrak Gharb, Tehran 1467686831, Iran.
authors.forename: Hossein
authors.initials: H
authors.lastname: Ghari
authors.affiliation: Organisch-Chemisches Institut, Universität Heidelberg , Im Neuenheimer Feld 270, Heidelberg 69120, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Arndt
authors.affiliation: Organisch-Chemisches Institut, Universität Heidelberg , Im Neuenheimer Feld 270, Heidelberg 69120, Germany.
authors.forename: A Stephen K
authors.initials: AS
authors.lastname: Hashmi
authors.affiliation: School of Physical Sciences (Chemistry), University of Tasmania , Private Bag 75, Hobart, Tasmania 7001, Australia.
authors.forename: Brian F
authors.initials: BF
authors.lastname: Yates
authors.affiliation: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University , Shahrak Gharb, Tehran 1467686831, Iran.|School of Physical Sciences (Chemistry), University of Tasmania , Private Bag 75, Hobart, Tasmania 7001, Australia.
authors.forename: Alireza
authors.initials: A
authors.lastname: Ariafard