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Eight-membered Palladacycles Derived from the Insertion of Olefines into the Pd–C Bond of Ortho-palladated Pharmaceuticals Phenethylamine and Phentermine. Synthesis of Stable Heck-type Intermediates Containing Accessible β-Hydrogens and its Use in the Synthesis of 2-Styryl-phenethylamines, Tetrahydroisoquinolines and Eight-membered Cyclic Amidines

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dc.contributor.advisorVicente, José
dc.contributor.authorVicente, José
dc.contributor.authorSaura-Llamas, Isabel
dc.contributor.authorGarcía-López, José-Antonio
dc.contributor.authorBautista, Delia
dc.contributor.departmentQuímica Inorgánica
dc.date.accessioned2024-01-17T11:09:16Z
dc.date.available2024-01-17T11:09:16Z
dc.date.created2010
dc.date.issued2010-09-13
dc.descriptionThis document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/om100738zes
dc.description.abstractThe ortho-metalated complexes derived from phenethylamine and phentermine [Pd(C,N-C6H4CH2CR2NH2-2)(μ-X)]2 (R = H, X = Br (A); R = Me, X = Cl (B)) react with olefins giving (1) the product of its insertion into the Pd–C bond, [Pd{C,NCH( R’)CH2C6H4CH2CR2NH2-2}(μ-X)]2 (olefin = CH2=CHR’; R = H, X = Cl, R’ = C(O)Me (1a), CO2Et (1c); R = Me, X = Cl, R’ = C(O)Me (1b), CO2Et (1d)), [Pd{C,NCH( C5H8)CHC6H4(CH2CMe2NH2)-2}(μ-Cl)]2 (olefin = norbornene, C5H8; 1e) or (2) the decomposition products of 1, i.e., Pd(0) and the complexes containing the arylated olefin, trans-[PdX2(NH2CR2CH2C6H4CH=CHPh-2)2] (olefin = styrene; R = H, X = Cl (3f); R = Me, X = Br (3g)). While complexes 1c and 1d can be isolated but decompose in solution to afford Pd(0) and the corresponding complexes 3 (R = H, X = Cl (3c); R = Me, X = Br (3d)), the others are surprisingly stable. Neutral ligands L cleave the bridge of complexes 1 to afford [Pd(C^N)X(L)] (2) (L = 4-methyl-pyridine (pic), NH3, NHEt2, PPh3, tBuNC, XyNC). Complexes 3 react with 1,10-phenanthroline (phen) to give [PdX2(phen)] and the orthovinylated arylalkylamine RCH=CHC6H4CH2CR2NH2-2 (R = H (4f), Me (4g)), which in the case of 3c or 3d can not be isolated as it undergoes an intramolecular hydroamination process to afford the tetrahydroisoquinoline 5c or 5d, respectively. To prepare the tetrahydroisoquinoline 5b, it is necessary to heat a mixture of complex 1b with one equiv of TlOTf. The eight-membered cyclic amidine 7d is obtained from thermal decomposition of complex cis-[Pd{C,N-CH(CO2Et)CH2C6H4CH2CR2NH2-2}(CNXy)2]OTf (8d), prepared by reaction of 2d-5 with TlOTf and XyNC. The amidinium salt 7e-HOTf is formed by refluxing in toluene a mixture of 2e-4 and TlOTf. The crystal structures of compounds 2a·CHCl3, 2b-1, 3 2d-3·1/3CH2Cl2, 2e-4·1/2CHCl3, 3d, 3g, 6 and 7e-HOTf have been determined by X-ray diffraction studies.es
dc.formatapplication/pdfes
dc.format.extent73es
dc.identifier.citationOrganometallics, 2010, 29, 4320-4338
dc.identifier.doihttps://doi.org/10.1021/om100738z
dc.identifier.issnPrint: 0276-7333
dc.identifier.issnElectronic: 1520-6041
dc.identifier.urihttp://hdl.handle.net/10201/137369
dc.languageenges
dc.publisherACSes
dc.relationMinisterio de Educación y Ciencia, FEDER Convocatoria: 2007, (CTQ2007-60808/BQU, C-Consolider), Fundación Séneca (04539/GERM/06)es
dc.relation.ispartofCompuestos organometálicos y de coordinación funcionalizados. Síntesis y reactividad funcionalizados (CTQ2007-60808/BQU, C-Consolider)es
dc.relation.publisherversionhttps://pubs.acs.org/doi/10.1021/om100738zes
dc.rightsinfo:eu-repo/semantics/openAccesses
dc.rightsAtribución 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectPaladioes
dc.subjectOrtometalaciónes
dc.subjectAminases
dc.subjectInserciónes
dc.subjectPrimary arylalkylamineses
dc.subjectPhenethylamineses
dc.subjectCyclopalladated complexeses
dc.subjectEight-membered palladacycleses
dc.subjectEight-membered cyclic amidineses
dc.subjectInsertion of alkeneses
dc.subjectHeck-type intermediateses
dc.subjectHeck reactiones
dc.subjectIsoquinolines,es
dc.subject2-vinyl-phenethylamineses
dc.subject.otherCDU::5 - Ciencias puras y naturaleses
dc.subject.otherCDU::5 - Ciencias puras y naturales::54 - Químicaes
dc.titleEight-membered Palladacycles Derived from the Insertion of Olefines into the Pd–C Bond of Ortho-palladated Pharmaceuticals Phenethylamine and Phentermine. Synthesis of Stable Heck-type Intermediates Containing Accessible β-Hydrogens and its Use in the Synthesis of 2-Styryl-phenethylamines, Tetrahydroisoquinolines and Eight-membered Cyclic Amidineses
dc.typeinfo:eu-repo/semantics/articlees
dspace.entity.typePublicationes
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