Gold-Catalyzed Access to 1H-Isochromenes: Reaction Development and Mechanistic Insight
| Autor: | Véronique Michelet, Jérôme Starck, Clément F. Heinrich, Eder Tomás-Mendivil, Jean-Claude Ortuno |
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| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Reaction mechanism 010405 organic chemistry General Chemistry 010402 general chemistry 01 natural sciences Aldehyde Combinatorial chemistry Catalysis Reductive elimination 0104 chemical sciences Benzaldehyde Solvent chemistry.chemical_compound chemistry Nucleophile Organic chemistry Methanol |
| Zdroj: | ResearcherID |
| ISSN: | 2155-5435 |
| Popis: | The gold-catalyzed domino cyclization/nucleophilic reaction of ortho-carbonylalkynylaryls has been studied. Thus, 2-(pyridin-2-ylethynyl)benzaldehyde has been chosen to isolate key intermediates that may take part in the reaction mechanism. Employing Hantzsch ester (HEH) as nucleophile, it has been impossible to isolate the corresponding gold–alkenyl specie; however, when methanol was used as solvent (and nucleophile), the expected chelate gold–vinyl complex was isolated and unambiguously characterized by X-ray analysis. When HEH is present in the alcoholic reaction mixture, isotopic studies show that the cleavage of the Au–C bond of gold–vinyl complex proceeds through a protodemetalation pathway, rather than a plausible metal–hydride reductive elimination mechanism. Finally, with the aim of broadening the scope of the cyclization/reduction reaction previously reported, we present that the catalytic system is robust and applicable for a diverse family of challenging substrates presenting ester, aldehyde, ... |
| Databáze: | OpenAIRE |
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