Metal-Free Intermolecular Coupling of Arenes with Secondary Amides: Chemoselective Synthesis of Aromatic Ketimines and Ketones, and N-Deacylation of Secondary Amides
| Autor: | Kai-Jiong Xiao, Ying-Hong Huang, Pei-Qiang Huang |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Ketone 010405 organic chemistry Chemistry Organic Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Aldehyde 0104 chemical sciences chemistry.chemical_compound Nucleophile Amide Electrophile Nitro Organic chemistry Nitrilium Chemoselectivity |
| Zdroj: | The Journal of Organic Chemistry. 81:9020-9027 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/acs.joc.6b01647 |
| Popis: | The direct transformation of common secondary amides into aromatic ketimines and aromatic ketones with C-C bond formation is described. The reaction can also be used for N-deacylation of secondary amides to release amines. This method consists of in situ amide activation with triflic anhydride and intermolecular capture of the resulting highly electrophilic nitrilium intermediate with an arene. The reaction is applicable to various kinds of secondary amides (electrophiles), but only electron-rich and moderately electron-rich arenes can be used as nucleophiles. Thanks to the use of bench stable arenes instead of reactive and basic organometallics as nucleophiles, the reaction proceeded with high chemoselectivity at the secondary amido group in the presence of a series of sensitive functional groups such as aldehyde, ketone, ester, cyano, nitro, and tertiary amido groups. The reaction can be viewed as a Friedel-Crafts-type reaction using secondary amides as acylating agents or as an intermolecular version of the Bischler-Napieralski reaction. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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