title: Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles.
abstract: The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2provided ketenimines through β-hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π-allyl Pd complex proceeded via an unusual η1-allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ-unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5-disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide.
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
authors.forename: Guanyinsheng
authors.initials: G
authors.lastname: Qiu
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
authors.forename: Mathias
authors.initials: M
authors.lastname: Mamboury
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
authors.forename: Jieping
authors.initials: J
authors.lastname: Zhu
keywords: isocyanides; ketenimines; palladium; tetrazoles; β,γ-unsaturated amides