title: α,β-Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5-Alkoxy Migration of 1,6-Enynes: Mechanisms and Applications.
abstract: 1,6-Enynes bearing OR groups at the propargyl position generate α,β-unsaturated gold(I)-carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3-diketones to give products of α-alkylation. The best migrating group is p-nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)-schisanwilsonene A has been accomplished. The different competitive reaction pathways have been delineated computationally.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Pilar
authors.initials: P
authors.lastname: Calleja
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Óscar
authors.initials: Ó
authors.lastname: Pablo
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Beatrice
authors.initials: B
authors.lastname: Ranieri
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Morgane
authors.initials: M
authors.lastname: Gaydou
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Anthony
authors.initials: A
authors.lastname: Pitaval
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: María
authors.initials: M
authors.lastname: Moreno
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Mihai
authors.initials: M
authors.lastname: Raducan
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain. aechavarren@iciq.es.|Departament de Química Analítica i Química Orgánica, Universitat Rovira i Virgili, C/ Marcel⋅li Domingo s/n, 43007, Tarragona, Spain. aechavarren@iciq.es.
authors.forename: Antonio M
authors.identifier: http://orcid.org/0000-0001-6808-3007
authors.initials: AM
authors.lastname: Echavarren
keywords: cycloisomerization; cyclopropanation; density functional calculations; gold; rearrangement