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Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of Ynamides.

  • Debrauwer V Université de Haute-Alsace, Université de Strasbourg, CNRS, LIMA, UMR 7042, 68000 Mulhouse, France.
  • Turlik A Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
  • Rummler L Université de Haute-Alsace, Université de Strasbourg, CNRS, LIMA, UMR 7042, 68000 Mulhouse, France.
  • Prescimone A Chemistry Department, University of Basel, Mattenstrasse 24a, 4058 Basel, Switzerland.
  • Blanchard N Université de Haute-Alsace, Université de Strasbourg, CNRS, LIMA, UMR 7042, 68000 Mulhouse, France.
  • Houk KN Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
  • Bizet V Université de Haute-Alsace, Université de Strasbourg, CNRS, LIMA, UMR 7042, 68000 Mulhouse, France.
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  • 2020-06-03
Published in:
  • Journal of the American Chemical Society. - 2020
Colloid and Surface Chemistry
Biochemistry
General Chemistry
Catalysis
English 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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  • English
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green
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https://sonar.ch/global/documents/92593
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