Direct Synthesis of Ketones from Methyl Esters by Nickel-Catalyzed Suzuki-Miyaura Coupling
| Autor: | Kendall N. Houk, Yan-Long Zheng, Stephen G. Newman, Omid Daneshfar, Xin Hong, Pei-Pei Xie |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Aryl Ether General Medicine General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Nucleophile chemistry Catalytic cycle Amide Reactivity (chemistry) Chemoselectivity Alkyl |
| Zdroj: | Angewandte Chemie (International ed. in English). 60(24) |
| ISSN: | 1521-3773 |
| Popis: | The direct conversion of alkyl esters to ketones has been hindered by the sluggish reactivity of the starting materials and the susceptibility of the product towards subsequent nucleophilic attack. We have now achieved a cross-coupling approach to this transformation using nickel, a bulky N-heterocyclic carbene ligand, and alkyl organoboron coupling partners. 65 alkyl ketones bearing diverse functional groups and heterocyclic scaffolds have been synthesized with this method. Catalyst-controlled chemoselectivity is observed for C(acyl)-O bond activation of multi-functional substrates bearing other bonds prone to cleavage by Ni, including aryl ether, aryl fluoride, and N-Ph amide functional groups. Density functional theory calculations provide mechanistic support for a Ni0 /NiII catalytic cycle and demonstrate how stabilizing non-covalent interactions between the bulky catalyst and substrate are critical for the reaction's success. |
| Databáze: | OpenAIRE |
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