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Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of Ynamides

preprint
submitted on 01.04.2020 and posted on 03.04.2020 by Vincent Debrauwer, Aneta Turlik, Lénaïc Rummler, Alessandro Prescimone, Nicolas Blanchard, Kendall N Houk, Vincent Bizet
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 hydro-metallation reactions of ynamides. Germylated and stannylated enamides are obtained with excellent alpha,E- or beta,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 metallated-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, the prevalence of a hydro-palladation pathway over a metal-palladation of the pi system of the ynamide was demonstrated.

Funding

Stereoselective transition metal-catalyzed hydrometallation of polarized C=C bonds – HydroMet

Agence Nationale de la Recherche

Find out more...

NSF CHE-1764328

NSF OCI-1053575

CNRS

Université de haute-Alsace

Université de Strasbourg

History

Email Address of Submitting Author

n.blanchard@unistra.fr

Institution

Université de Haute-Alsace, Université de Strasbourg, CNRS

Country

France

ORCID For Submitting Author

0000-0002-3097-0548

Declaration of Conflict of Interest

The authors declare no competing financial interests.

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