title: Intramolecular Pd-mediated processes of amino-tethered aryl halides and ketones: insight into the ketone alpha-arylation and carbonyl-addition dichotomy. A new class of four-membered azapalladacycles.
abstract: 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 omega-(2-haloanilino) alkanones, enolate arylation and addition to the carbonyl group, have been observed, while omega-(2-halobenzylamino) alkanones exclusively underwent the enolate arylation process. The dichotomy between ketone alpha-arylation and carbonyl-addition in the reactions of omega-(2-haloanilino) alkanones has been rationalized by the intermediacy of unprecedented four-membered azapalladacycles, from which X-ray data and chemical behavior are reported.
authors.affiliation: Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII s/n, 08028-Barcelona, Spain.
authors.forename: Daniel
authors.initials: D
authors.lastname: Solé
authors.forename: Lluís
authors.initials: L
authors.lastname: Vallverdú
authors.forename: Xavier
authors.initials: X
authors.lastname: Solans
authors.forename: Mercè
authors.initials: M
authors.lastname: Font-Bardía
authors.forename: Josep
authors.initials: J
authors.lastname: Bonjoch