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Keteniminium-Driven Umpolung Difunctionalization of Ynamides |
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| Authors: | Shubham Dutta Shengwen Yang Rajeshwer Vanjari Rajendra K. Mallick Vincent Gandon Prof. Dr. Akhila K. Sahoo |
| Affiliation: | 1. School of Chemistry, University of Hyderabad, Hyderabad, India;2. Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Université Paris-Saclay, Bâtiment 420, 91405 Orsay cedex, France Laboratoire de Chimie Moléculaire (LCM), CNRS UMR 9168, Ecole Polytechnique, Université Paris-Saclay, route de Saclay, 91128 Palaiseau cedex, France These authors contributed equally to this work.;3. Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Université Paris-Saclay, Bâtiment 420, 91405 Orsay cedex, France |
| Abstract: | A three-component Pd-catalyzed coupling of ynamides, aryl diazonium salts, and aryl boronic acids for the synthesis of novel triaryl-substituted enamides is described. This transformation represents the first example of an umpolung regioselective unsymmetrical syn-1,2-diarylation/aryl-olefination of ynamides. The aryl moieties of the diazonium salt (electrophile) and boronic acid (nucleophile) are explicitly incorporated in the electrophilic α- and nucleophilic β-position, respectively, of the ynamide, resulting in a single isomer of the N-bearing tetrasubstituted olefin. The scope is broad (68 examples), showing excellent functional-group tolerance. DFT calculations substantiate the rationale of the mechanistic cycle and the regioselectivity. The chemoselectivity and synthetic potential of the enamide products were also studied. |
| Keywords: | Mehrkompontentn-Reaktionen Palladium Reaktionsmechanismen Synthesemethoden Umpolung |