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Article Dans Une Revue Journal of the American Chemical Society Année : 2020

Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of Ynamides

Résumé

Ynamides are fascinating small molecules with complementary reactivities under radical, ionic, and metal-catalyzed conditions. We report herein synthetic and DFT investigations of palladium-catalyzed ligand-controlled regiodivergent hydrometalation reactions of ynamides. Germylated and stannylated enamides are obtained with excellent α,E- or β,E-selectivities and a broad functional group tolerance. Such a regiodivergent palladium-catalyzed process is unique in ynamide chemistry and allows for the elaboration of metalated enamides that are useful building blocks for cross-coupling reactions or heterocyclic chemistry. DFT calculations fully support the experimental data and demonstrate the crucial roles of the trans-geometry of the [H-Pd(L)-Ge] complex, as well as of the steric requirements of the phosphine ligand. In addition, these calculations support the prevalence of a hydro-palladation pathway over a metal palladation of the π system of the ynamide.
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Dates et versions

hal-02868667 , version 1 (06-11-2020)

Identifiants

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Vincent Debrauwer, Aneta Turlik, Lénaic Rummler, Alessandro Prescimone, Nicolas Blanchard, et al.. Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of Ynamides. Journal of the American Chemical Society, 2020, 142 (25), pp.11153-11164. ⟨10.1021/jacs.0c03556⟩. ⟨hal-02868667⟩
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