Título:
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NH2 as a directing group: from the unexpected cyclopalladation of aminoesters to the preparation of benzolactams by Pd(II)-catalyzed carbonylation of N-unprotected arylethylamines
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Autor/a:
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Albert Mach, Joan; Ariza Piquer, Xavier; Calvet Pallàs, Maria Teresa; Font Bardia, Ma. Mercedes; García Gómez, Jordi; Granell Sanvicente, Jaime Ramón; Lamela, Andrea; López, Blanca; Martínez López, Manuel, 1957-; Ortega, Laura; Rodríguez Ramírez, Aleix; Santos, David
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Otros autores:
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Universitat de Barcelona |
Abstract:
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An unusual NH2-directed Pd(II)-catalytic carbonylation of quaternary aromatic α-amino esters to yield benzolactams has been developed. The steric hindrance around the amino group is pivotal for the success of the process. The stoichiometric cyclometallation of a variety amino esters has been studied in order to evaluate the influence of the different variables (size of the metallacycle, aromatic ring substituents, and steric bulk) in the process, and a complete kinetico-mechanistic study of the cyclopalladation process has been carried out. The experimental results indicate that the full substitution of the carbon in the α position of the amino esters plays an important role in their cyclopalladation reaction. The reaction shows a strong bias to 6-membered lactams over the 5-membered analogues, which can be explained by a greater reactivity of the six-membered palladacycles. |
Materia(s):
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-Pal·ladi (Element químic) -Cinètica química -Compostos organometàl·lics -Cristal·lografia -Catàlisi -Palladium -Chemical kinetics -Organometallic compounds -Crystallography -Catalysis |
Derechos:
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(c) American Chemical Society , 2013
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Tipo de documento:
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Artículo Artículo - Versión aceptada |
Editor:
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American Chemical Society
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