Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles
The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2 provided ketenimines through b-hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the p-allyl Pd complex proceeded via an unusual h1-allyl Pd species. The resulting ketenimines were hydrolyzed to b,g-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.
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Qiu, G., Mamboury, M., Wang, Q., & Zhu, J. (2016). Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles. Angewandte Chemie International Edition, 55(49), 15377–15381. https://doi.org/10.1002/anie.201609034
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WOS:000389224000036
2016
55
49
15377
15381
REVIEWED
EPFL