Rhodium-Catalyzed Copper-Assisted Intermolecular Domino C−H Annulation of 1,3-Diynes with Picolinamides: Access to Pentacyclic π-Extended Systems

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dc.contributor.author Martínez, Ángel Manu
dc.contributor.author Alonso, Inés
dc.contributor.author Rodríguez, Nuria
dc.contributor.author Gómez Arrayás, Ramón
dc.contributor.author Carretero, Juan C.
dc.contributor.other UAM. Departamento de Química Orgánica es_ES
dc.contributor.other Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem) es_ES
dc.date.accessioned 2019-05-09T10:57:35Z
dc.date.available 2019-05-09T10:57:35Z
dc.date.issued 2019-03-28
dc.identifier.citation Chemistry - A European Journal 25.22 (2019): 5733-5742 en_US
dc.identifier.issn 0947-6539 (print) en_US
dc.identifier.issn 1521-3765 (online) en_US
dc.identifier.uri http://hdl.handle.net/10486/687485
dc.description This is the peer reviewed version of the following article: Chemistry - A European Journal 25.22 (2019): 5733-5742, which has been published in final form at https://doi.org/10.1002/chem.201900162. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions en_US
dc.description.abstract A new mode of reactivity of 1,3-diynes in rhodium-catalyzed oxidative annulation reactions has enabled the rapid assembly of extended π systems from readily available picolinamide derivatives. The process involves a double C−H bond activation and the iterative annulation of two 1,3-diyne units, with each alkyne moiety engaged in an orchestrated insertion sequence with high regiocontrol, leading to the formation of five new C−C bonds and the construction of four fused rings in a single operation. Either isoquinoline-1-carboxamides or fused polycyclic systems can be accessed by a switch in the regioselectivity of the second diyne insertion depending on the reaction conditions. DFT theoretical calculations have elucidated that the cooperative participation of both rhodium and copper in substrate activation, favored in the presence of excess of the copper(II) salt, is key to such a reversal of regioselectivity and subsequent multiple cyclization leading to fused polycyclic products. The role of copper was found to be essential in assisting both multiple insertion and rhodium-walking sequences, with the implication of intermediates with a Rh−Cu bond (2.60 Å) en_US
dc.description.sponsorship We thank the Spanish Ministerio de Economía, Industria y Competitividad (MINECO, Grants CTQ2012-35790 and CTQ2015-66954-P, MINECO/FEDER, UE) for financial support. N.R. thanks the MICINN for a Ramón y Cajal contract and the European Commission for a for a Marie Curie Career Integration Grant (CIG: CHAAS-304085). The Centro de Computación Científica (UAM) is acknowledged for generous allocation of computer time. We also thank Dr J. Lloret for helpful discussions en_US
dc.format.extent 14 pag. en_US
dc.format.mimetype application/pdf en
dc.language.iso eng en
dc.publisher Wiley-VCH Verlag en_US
dc.relation.ispartof Chemistry - A European Journal en_US
dc.rights © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim en_US
dc.subject.other Alkynes en_US
dc.subject.other Annulation en_US
dc.subject.other Fused-ring systems en_US
dc.subject.other Nitrogen heterocycles en_US
dc.subject.other Reaction mechanisms en_US
dc.subject.other Rhodium en_US
dc.title Rhodium-Catalyzed Copper-Assisted Intermolecular Domino C−H Annulation of 1,3-Diynes with Picolinamides: Access to Pentacyclic π-Extended Systems en_US
dc.type article en
dc.subject.eciencia Química es_ES
dc.date.embargoend 2020-03-28
dc.relation.publisherversion https://doi.org/10.1002/chem.201900162 es_ES
dc.identifier.doi 10.1002/chem.201900162 es_ES
dc.identifier.publicationfirstpage 5733 es_ES
dc.identifier.publicationissue 22 es_ES
dc.identifier.publicationlastpage 5742 es_ES
dc.identifier.publicationvolume 25 es_ES
dc.relation.projectID Gobierno de España. CTQ2012-35790 es_ES
dc.relation.projectID Gobierno de España. CTQ2015-66954-P es_ES
dc.relation.projectID info:eu-repo/grantAgreement/EC/FP7/304085 en_US
dc.type.version info:eu-repo/semantics/acceptedVersion en
dc.rights.accessRights openAccess en
dc.authorUAM Gómez Arrayas, Ramón Jesús (260197)

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