117352 20230622083326.0 doi 10.1002/chem.202101414 sideral 126859 ART-2021-126859 eng Azpíroz R. (orcid)0000-0001-7904-2729 Preparation of Butadienylpyridines by Iridium-NHC-Catalyzed Alkyne Hydroalkenylation and Quinolizine Rearrangement 2021 Access copy available to the general public Unrestricted Iridium(I) N-heterocyclic carbene complexes of formula Ir(¿2O, O’-BHetA)(IPr)(¿2-coe) [BHetA=bis-heteroatomic acidato, acetylacetonate or acetate; IPr=1, 3-bis(2, 6-diisopropylphenyl)imidazolin-2-carbene; coe=cyclooctene] have been prepared by treating Ir(¿2O, O’-BHetA)(¿2-coe)2 complexes with IPr. These complexes react with 2-vinylpyridine to afford the hydrido-iridium(III)-alkenyl cyclometalated derivatives IrH(¿2O, O’-BHetA)(¿2N, C-C7H6N)(IPr) through the iridium(I) intermediate Ir(¿2O, O’-BHetA)(IPr)(¿2-C7H7N). The cyclometalated IrH(¿2O, O’-acac)(¿2N, C–C7H6N)(IPr) complex efficiently catalyzes the hydroalkenylation of aromatic and aliphatic terminal alkynes and enynes with 2-vinylpyridine to afford 2-(4R-butadienyl)pyridines with Z, E configuration as the major reaction products (yield up to 89 %). In addition, unprecedented (Z)-2-butadienyl-5R-pyridine derivatives have been obtained as minor reaction products (yield up to 21 %) from the elusive 1Z, 3gem-butadienyl hydroalkenylation products. These compounds undergo a thermal 6p-electrocyclization to afford bicyclic 4H-quinolizine derivatives that, under catalytic reaction conditions, tautomerize to 6H-quinolizine to afford the (Z)-2-(butadienyl)-5R-pyridine by a retro-electrocyclization reaction. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/semantics/openAccess by-nc-nd http://creativecommons.org/licenses/by-nc-nd/3.0/es/ 5.02 2021 CHEMISTRY, MULTIDISCIPLINARY 64 / 180 = 0.356 2021 Q2 T2 1.343 2021 Chemistry (miscellaneous) 2021 Q1 Catalysis 2021 Q1 9.1 2021 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Greger I. Oro L.A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Passarelli V. Universidad de Zaragoza (orcid)0000-0002-1735-6439 Castarlenas R. (orcid)0000-0003-4460-8678 Pérez-Torrente J.J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 27, 46 (2021), 11868-11878 Chemistry (Weinh.) Chemistry - A European Journal 0947-6539 4431920 http://zaguan.unizar.es/record/117352/files/texto_completo.pdf Versión publicada 2316921 http://zaguan.unizar.es/record/117352/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:117352 articulos driver 2023-06-21-15:03:36 ARTICLE