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Intramolecular Pd-Mediated Processes of Amino-Tethered Aryl Halides and Ketones:  Insight into the Ketone α-Arylation and Carbonyl-Addition Dichotomy. A New Class of Four-Membered Azapalladacycles

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journal contribution
posted on 18.01.2003, 00:00 by Daniel Solé, Lluís Vallverdú, Xavier Solans, Mercè Font-Bardía, Josep Bonjoch
An exploration of the scope and limitations of Pd(0)-catalyzed intramolecular coupling reactions of amino-tethered aryl halides and ketones has been conducted. Two different and competitive reaction pathways starting from ω-(2-haloanilino) alkanones, enolate arylation and addition to the carbonyl group, have been observed, while ω-(2-halobenzylamino) alkanones exclusively underwent the enolate arylation process. The dichotomy between ketone α-arylation and carbonyl-addition in the reactions of ω-(2-haloanilino) alkanones has been rationalized by the intermediacy of unprecedented four-membered azapalladacycles, from which X-ray data and chemical behavior are reported.