Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement of aryl formates (Articolo in rivista)

Type
Label
  • Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement of aryl formates (Articolo in rivista) (literal)
Anno
  • 2008-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1002/poc.1356 (literal)
Alternative label
  • Bagno, A., Kantlehner, W., Saielli, G. (2008)
    Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement of aryl formates
    in Journal of physical organic chemistry (Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Bagno, A., Kantlehner, W., Saielli, G. (literal)
Pagina inizio
  • 682 (literal)
Pagina fine
  • 687 (literal)
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  • 21 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Dipartimento di Scienze Chimiche, Universita` degli Studi di Padova, Via Marzolo, 1-35131 Padova, Italy Institut fu¨r Organische Chemie der Universita¨t Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany Istituto per la Tecnologia delle Membrane del CNR, Sezione di Padova, Via Marzolo, 1-35131 Padova, Italy (literal)
Titolo
  • Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement of aryl formates (literal)
Abstract
  • We present an NMR and DFT investigation of the reaction of phenyl formate with 3-methoxyphenol and 3,5-dimethoxyphenol with excess BCl3. The products obtained (3-methoxy- and 3,5-dimethoxy-salicylaldehyde, respectively) are the same as those resulting from the Fries rearrangement of 3-methoxy- and 3,5-dimethoxy-phenyl formate. These results represent a novel regioselective synthetic route to aromatic aldehydes, using phenyl formate as a source of formylating agent. They also unambiguously prove that the Fries rearrangement of aryl formates (that we recently investigated in J. Org. Chem. 71, 9331-9340, 2006) is intermolecular: the intermediate formyl chloride is released in situ and, in turn, it formylates the intermediate dichloroborate ester of 3-methoxy- and 3,5-dimethoxy-phenol in a second independent step. The --BCl2 moiety bound to the aryl oxygen of the substituted phenol interacts with the formyl chloride strongly favouring the ortho substitution. (literal)
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