Pd-Catalyzed Carbonylation of Acyl Azides
| Autor: | Wenxu Chang, Lei Jiao, Zongyang Li, Baoliang Huang, Peng Wang, Chenhui Yuan, Bin Fu, Zhenhua Zhang, Shiyang Xu |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
inorganic chemicals
010405 organic chemistry Chemistry Organic Chemistry Substrate (chemistry) chemistry.chemical_element 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis chemistry.chemical_compound Amine gas treating Azide Palladium catalyst Carbonylation Palladium |
| Zdroj: | The Journal of Organic Chemistry. 84:9497-9508 |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | Pd-catalyzed reactions of azides with CO to access an isocynate intermediate have been developed extensively in recent years. However, the catalytic carbonylation of sensitive acyl azides has not been reported. Herein, we report a simple Pd-catalyzed carbonylation reaction of acyl azides with broad substrate scope, high efficiency, and simple operation under mild conditions, which provides facile access to acyl ureas. In addition, a mechanistic study was carried out by both experiment and DFT calculation. Control experiments and kinetic study revealed that the real active palladium species were Pd(0). The result of kinetic study suggested that palladium catalyst, azide, and CO were all involved in the turnover-limiting step except for amine. Further DFT study suggested that an unprecedented five-membered palladacycle intermediate was the key intermediate in the carbonylation reaction. |
| Databáze: | OpenAIRE |
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