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oai:recercat.cat:10256/121942024-06-18T13:50:58Zcom_2072_452955com_2072_2054col_2072_453073

The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes Garcia Borràs, Marc Cerón, Maira R. Osuna Oliveras, Sílvia Izquierdo, Marta Luis Luis, Josep Maria Echegoyen, Luis A. Solà i Puig, Miquel Ministerio de Economía y Competitividad (Espanya) Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca Aromaticitat (Química) Aromaticity (Chemistry) Fullerenes Ful·lerens Funcional de densitat, Teoria del Density functionals Química supramolecular Supramolecular chemistry Bingel-Hirsch, Reacció de Bingel-Hirsch reaction Ciclització (Química) Ring formation (Chemistry) Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 7, p. 2420-2423. DOI http://dx.doi.org/10.1002/ange.201509057 In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h-C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h-C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes We are grateful to the Spanish MINECO (CTQ2014-54306-P, CTQ2014-52525-P, CTQ2014-59212-P, and JdlC contract to S.O.), the Catalan DIUE (2014SGR931, ICREA Academia 2014 Award to M.S. and XRQTC), and the FEDER fund (UNGI10-4E-801) for financial support. M.G.-B. thanks the Spanish MECD for a PhD grant (AP2010-2517) and S.O. the European Commission for CIG project (FP7-PEOPLE-2013- CIG-630978). CESCA and BSC-CNS are acknowledged. M.R.C, M.I. and L.E. thanks the NSF for generous support of this work under grant (CHE-1408865) and to the NSFPREM program (DMR-1205302). The Robert A. Welch Foundation is also gratefully acknowledged for an endowed chair to L.E. (grant AH-0033) info:eu-repo/date/embargoEnd/2026-01-01 info:eu-repo/date/embargoEnd/2026-01-01 2016 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion http://hdl.handle.net/10256/12194 http://hdl.handle.net/10256/12194 eng info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201509057 info:eu-repo/semantics/altIdentifier/issn/1433-7851 info:eu-repo/semantics/altIdentifier/eissn/1521-3773 info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/ info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/ AGAUR/2014-2016/2014 SGR-931 info:eu-repo/grantAgreement/EC/FP7/630978/EU/Computational Exploration of Directed Evolution rules for tuning enzymatic activities/DIREVENZYME Tots els drets reservats info:eu-repo/semantics/embargoedAccess application/pdf Wiley-VCH Verlag © Angewandte Chemie International Edition, 2016, vol. 55, núm. 7, p. 2374-2377 Articles publicats (D-Q)