Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: Covalent bond formation (Articolo in rivista)

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Label
  • Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: Covalent bond formation (Articolo in rivista) (literal)
Anno
  • 2013-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/jo400489m (literal)
Alternative label
  • F. Ghirga, I. D'Acquarica, G. Delle Monache, L. Mannina, C. Molinaro, L. Nevola, A.P. Sobolev, M. Pierini, B. Botta (2013)
    Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: Covalent bond formation
    in Journal of organic chemistry (Online)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • F. Ghirga, I. D'Acquarica, G. Delle Monache, L. Mannina, C. Molinaro, L. Nevola, A.P. Sobolev, M. Pierini, B. Botta (literal)
Pagina inizio
  • 6935 (literal)
Pagina fine
  • 6946 (literal)
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  • http://www.scopus.com/inward/record.url?eid=2-s2.0-84880539151&partnerID=q2rCbXpz (literal)
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  • 78 (literal)
Rivista
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  • 14 (literal)
Note
  • Scopu (literal)
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  • Dipartimento di Chimica e Tecnologie Del Farmaco, Sapienza Università di Roma, P. le Aldo Moro 5, 00185 Roma, Italy; Laboratorio di Risonanza Magnetica Annalaura Segre, Istituto di Metodologie Chimiche, Area della Ricerca di Roma, Via Salaria km 29.300, 00015 Monterotondo, Italy; Institut de Recerca Biomèdica (IRB-PCB), Barcelona, Spain (literal)
Titolo
  • Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: Covalent bond formation (literal)
Abstract
  • Resorc[4]arenes 1 and 2, which previously proved to entrap NO+ cation within their cavities under conditions of host-to-guest excess, were treated with a 10-fold excess of NOBF4 salt in chloroform. Kinetic and spectral UV-visible analyses revealed the formation of isomeric 1:2 complexes as a direct evolution of the previously observed event. Accordingly, three-body 1-(NO+)2 and 2-(NO+)2 adducts were built by MM and fully optimized by DFT calculations at the B3LYP/ 6-31G(d) level of theory. Notably, covalent nitration products 4, 5 and 6, 7 were obtained by reaction of NOBF4 salt with host 1 and 2, respectively, involving macrocycle ring-opening and insertion of a nitro group in one of the four aromatic rings. In particular, compounds 4 and 6, both containing a trans-double bond in the place of the methine bridge, were oxidized to aldehydes 5 and 7, respectively, after addition of water to the reaction mixture. Calculation of the charge and frontier orbitals of the aromatic donor (HOMO) and the NO+ acceptor (LUMO) clearly suggests an ipso electrophilic attack by a first NO+ unit on the resorcinol ring, mediated by the second NO+ unit. (literal)
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