Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
Iannace, Valentina (Universitat de Girona. Departament de Química)
Sabrià, Clar (Universitat de Girona. Departament de Química)
Xu, Youzhi (University of Ulm)
Von Delius, Max (University of Ulm)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)
Feixas, Ferran (Universitat de Girona. Departament de Química)
Ribas, Xavi (Universitat de Girona. Departament de Química)

Date:	2024
Abstract:	Isomer-pure functionalized fullerenes are required to boost the development of fullerene chemistry in any field, but their multiple functionalization renders a mixture of regioisomers that are very difficult to purify by chromatography. For the specific case of C, its nonspherical geometry makes its regioselective functionalization more challenging than that of spherical C. In this work, the supramolecular mask approach is applied for the first time to C, which is encapsulated in two different nanocapsules to achieve the Bingel bis-cyclopropanation at α-bonds of opposite poles. Based on the tetragonal prismatic geometry imposed by the smaller supramolecular mask tested, the obtained major bis-adduct is completely reversed (major 5 o'clock) compared to bare C functionalization (major 2 o'clock). Moreover, by further restricting the accessibility of C using a three-shell Matryoshka mask and dibenzyl-bromomalonate, a single regiospecific 2 o'clock bis-isomer is obtained, owing to the perfect complementarity of the mask and the addend steric properties. The outcome of the reactions is fully explained at the molecular level by means of a thorough molecular dynamics (MD) study of the accessibility of the α-bonds to produce the different bis-adducts.
Grants:	Agencia Estatal de Investigación PID2019-104498GB-I00 Agencia Estatal de Investigación PID2022-136970NB-I00 Agencia Estatal de Investigación TED2021-130573B-I00 Agencia Estatal de Investigación RTI2018-101032-J100 Agencia Estatal de Investigación RYC2020-029552-I Agencia Estatal de Investigación PID2022-141676NB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00475 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00487
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Journal of the American Chemical Society, Vol. 146, Issue 8 (February 2024) , p. 5186-5194, ISSN 1520-5126

DOI: 10.1021/jacs.3c10808
PMID: 38311922

9 p, 6.0 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles