Oxyfunctionalization of Non-Natural Targets by dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties (Articolo in rivista)

Type
Label
  • Oxyfunctionalization of Non-Natural Targets by dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties (Articolo in rivista) (literal)
Anno
  • 2003-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/jo034768o (literal)
Alternative label
  • D'Accolti L., Dinoi A., Fusco C., Russo A., Curci R. (2003)
    Oxyfunctionalization of Non-Natural Targets by dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties
    in Journal of organic chemistry
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • D'Accolti L., Dinoi A., Fusco C., Russo A., Curci R. (literal)
Pagina inizio
  • 7806 (literal)
Pagina fine
  • 7810 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://pubs.acs.org/doi/abs/10.1021/jo034768o (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 68 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#descrizioneSinteticaDelProdotto
  • The powerful methyl(trifluoromethyl)dioxirane (1b) was employed to achieve the direct oxyfunctionalization of 2,4-didehydroadamantane (5), spiro[cyclopropane-1,2'-adamantane] (9), spiro[2.5]octane (17), and bicyclo[6.1.0]nonane (19). The product distributions observed show that cyclopropyl activation of alpha-C-H bonds largely prevails when no tertiary C-H are present. The application of dioxirane 1b to polycyclic alkanes demonstrates the relevance of relative orientation of the cyclopropane moiety with respect to the proximal C-H undergoing oxidation. (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Dipartimento Chimica, Universita` di Bari, and C.N.R.-Istituto di Chimica dei Composti Organometallici (ICCOM), Bari Section (literal)
Titolo
  • Oxyfunctionalization of Non-Natural Targets by dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties (literal)
Abstract
  • The powerful methyl(trifluoromethyl)dioxirane (1b) was employed to achieve the direct oxyfunctionalization of 2,4-didehydroadamantane (5), spiro[cyclopropane-1,2'-adamantane] (9), spiro[2.5]octane (17), and bicyclo[6.1.0]nonane (19). The results are compared with those attained in the analogous oxidation of two alkylcyclopropanes, i.e., n-butylcyclopropane (11) and (3-methyl-butyl)-cyclopropane (14). The product distributions observed for 11 and 14 show that cyclopropyl activation of alpha-C-H bonds largely prevails when no tertiary C-H are present; however, in the oxyfunctionalixation of 14 cyclopropyl activation competes only mildly with hydroxylation at the tertiary C-H. The application of dioxirane 1b to polycyclic alkanes possessing a sufficiently rigid framework (such as 5 and 9) demonstrates the relevance of relative orientation of the cyclopropane moiety with respect to the proximal C-H undergoing oxidation. At one extreme, as observed in the oxidation of rigid spiro compound 9, even bridgehead tertiary C-H's become deactivated by the proximal cyclopropyl moiety laying in the unfavorable \"eclipsed\" (perpendicular) orientation; at the other end, a cyclopropane moiety constrained in a favorable \"bisected\" orientation (as for didehydroadamantane 5) can activate an \"alpha\" methylene CH2 to compete effectively with dioxirane O-insertion into tertiary C-H bonds. Comparison with literature reports describing similar oxidations by dimethyldioxirane (1a) demonstrate that methyl(trifluoromethyl)dioxirane (1b) presents similar selectivity and remarkably superior reactivity. (literal)
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