Pinto Alexandre, Kaiser Daniel, Maryasin Boris, Di Mauro Giovanni, González Leticia, Maulide Nuno
Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.
Chemistry. 2018 Feb 16;24(10):2515-2519. doi: 10.1002/chem.201706063. Epub 2018 Jan 24.
Organic synthesis boasts a wide array of reactions involving either radical species or ionic intermediates. The combination of radical and polar species, however, has not been explored to a comparable extent. Herein we present the hydrative aminoxylation of ynamides, a reaction which can proceed by either a polar-radical crossover mechanism or through a rare cationic activation. Common to both processes is the versatility of the persistent radical TEMPO and its oxidised oxoammonium derivative TEMPO . The unique mechanisms of these processes are elucidated experimentally and by in-depth DFT-calculations.
有机合成拥有大量涉及自由基物种或离子中间体的反应。然而，自由基和极性物种的组合尚未得到同等程度的探索。在此，我们展示了烯酰胺的水合氨氧基化反应，该反应可以通过极性 - 自由基交叉机制或通过罕见的阳离子活化进行。这两个过程的共同之处在于持久性自由基TEMPO及其氧化的氧鎓铵衍生物TEMPO的多功能性。通过实验和深入的密度泛函理论（DFT）计算阐明了这些过程的独特机制。
