Mechanism of Au(III)-Mediated Alkoxycyclization of a 1,6-Enyne
| Autor: | Máté Erdélyi, Dániel Csókás, Anne Fiksdahl, Imre Pápai, Ann Christin Reiersølmoen |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Denticity Enyne Ligand Alkyne Homogeneous catalysis General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Combinatorial chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry chemistry Pyridine Counterion |
| Zdroj: | Journal of the American Chemical Society. 141:18221-18229 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.9b09108 |
| Popis: | Gold-mediated homogeneous catalysis is a powerful tool for construction of valuable molecules and has lately received growing attention. Whereas Au(I)-catalyzed processes have become well established, those mediated by Au(III) have so far barely been explored, and their mechanistic understanding remains basic. Herein, we disclose the combined NMR spectroscopic, single-crystal X-ray crystallographic, and computational (DFT) investigation of the Au(III)-mediated alkoxycyclization of a 1,6-enyne in the presence of a bidentate pyridine-oxazoline ligand. The roles of the counterion, the solvent, and the type of Au(III) complex have been assessed. Au(III) is demonstrated to be the active catalyst in alkoxycyclization. Alkyne coordination to Au(III) involves decoordination of the pyridine nitrogen and is the rate-limiting step. |
| Databáze: | OpenAIRE |
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