Ketenimines from Isocyanides and Allyl Carbonates: Palladium‐Catalyzed Synthesis of β,γ‐Unsaturated Amides and Tetrazoles |
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| Authors: | Dr Qian Wang Prof?Dr Jieping Zhu |
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| Affiliation: | Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland |
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| Abstract: | The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2 provided 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. |
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| Keywords: | isocyanides ketenimines palladium tetrazoles β γ -unsaturated amides |
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