Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 25, Pages 11153-11164Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c03556
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Funding
- ANR HydroMet project of the French National Research Agency (ANR) [ANR-18-CE07-0020]
- CNRS
- Universite de Haute-Alsace
- Universite de Strasbourg
- National Science Foundation [CHE-1764328, OCI-1053575]
- Agence Nationale de la Recherche (ANR) [ANR-18-CE07-0020] Funding Source: Agence Nationale de la Recherche (ANR)
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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 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 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 it system of the ynamide.
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