Rhodium-Catalyzed Copper-Assisted Intermolecular Domino C−H Annulation of 1,3-Diynes with Picolinamides: Access to Pentacyclic π-Extended Systems
Entity
UAM. Departamento de Química Orgánica; UAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)Publisher
Wiley-VCH VerlagDate
2019-03-28Citation
10.1002/chem.201900162
Chemistry - A European Journal 25.22 (2019): 5733-5742
ISSN
0947-6539 (print); 1521-3765 (online)DOI
10.1002/chem.201900162Funded by
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 discussionsProject
Gobierno de España. CTQ2012-35790; Gobierno de España. CTQ2015-66954-P; info:eu-repo/grantAgreement/EC/FP7/304085Editor's Version
https://doi.org/10.1002/chem.201900162Subjects
Alkynes; Annulation; Fused-ring systems; Nitrogen heterocycles; Reaction mechanisms; Rhodium; QuímicaNote
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 VersionsRights
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimAbstract
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)
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Google Scholar:Martínez, Ángel Manu
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Alonso Montero, María Inés
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Rodríguez Garrido, Nuria
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Gómez Arrayas, Ramón Jesús
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Carretero Gonzálvez, Juan Carlos
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