Rodríguez Aleix, Albert Joan, Ariza Xavier, Garcia Jordi, Granell Jaume, Farràs Jaume, La Mela Andrea, Nicolás Ernesto
Departament de Química Orgànica, Facultat de Química, Universitat de Barcelona , Martí i Franquès 1, 08028 Barcelona, Spain.
J Org Chem. 2014 Oct 17;79(20):9578-85. doi: 10.1021/jo501658s. Epub 2014 Oct 1.
Tetrahydro-3-benzazepines and tetrahydroisoquinolines are synthesized in one step from allenes and phenylethylamines or benzylamines, respectively. Mechanistically, it is assumed that activation of a C-H bond of an aromatic ring with Pd(II) occurs, directed by the primary amine, leading to the formation of a palladacycle into which an allene then undergoes insertion. The resulting π-allyl intermediate cyclizes to the products by an intramolecular allylic alkylation. The process is particularly useful with 2,3-butadienoates and amines having a quaternary carbon at the α-position.
四氢-3-苯并氮杂卓和四氢异喹啉分别由丙二烯与苯乙胺或苄胺一步合成。从机理上推测，在伯胺的导向作用下，芳环的C-H键被Pd(II)活化，导致形成一个钯杂环，然后丙二烯插入其中。生成的π-烯丙基中间体通过分子内烯丙基烷基化环化生成产物。该方法对于2,3-丁二烯酸酯和在α位具有季碳的胺特别有用。
