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Rendiconti Lincei

, Volume 1, Issue 3, pp 299–305 | Cite as

Modelli sintetici del Citocromo P-450

  • Pier Lucio Anelli
  • Stefano Banfi
  • Fernando Montanari
  • Silvio Quici
Chimica organica

Riassunto

Un modello sintetico del Citocromo P-450.è stato ottenuto collegando il residuo delľN-esilimidazolo alla Mn(III)-tetra(2,6-diclorofenil) porfirina mediante un ponte di ossigeno che sostituisce uno degli 8 atomi di Cl. Questa porfirina unisce un’alta resistenza agli ossidanti con un’elevata attività catalitica. Epossidazioni di olefine, condotte in doppia fase H2O—CH2C12 e promosse da NaOCl a pH 10.5 o da H2O2-30%-acido benzoico a pH 4.5, procedono a velocità di 6-50 cicli/min a 0 °C in assenza di basi eterocicliche aggiuntive. Ľintroduzione di un gruppo COOH a fine catena al posto delľanello imidazolico fornisce un catalizzatore altrettanto efficace per le epossidazioni condotte con H2O2-30%, la cui attivazione non richiede ľaggiunta di un acido carbossilico esterno.

Synthetic models of Cytochrome P-450

Abstract

A synthetic model of Cytochrome P-450 has been obtained connecting the residue of N-hexyl imidazole to Mn(III)-tetra(2,6-dichlorophenyl) porphyrin by an oxygen bridge which substitutes one out of eight Cl atoms. This porphyrin combines a high resistance to the oxidants with a high catalytic activity. Olefin epoxidations, carried out under H2O—CH2C12 two-phase conditions and promoted by NaOCl at pH 10.5 or by 30%-H2O2-benzoic acid at pH 4.5, proceed at 6-50 turnovers/min rates at 0 °C in the absence of additional heterocyclic bases. The introduction of a COOH group at the end of the chain instead of the imidazole ring affords a catalyst which is also very efficient in the epoxidations promoted by 30%-H2O2, whose activation does not require any additional carboxylic acid.

Key words

Biomimetic olefin epoxidations Tailed Mn(III)-tetraaryl porphyrins H2O2 activation 

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Copyright information

© Accademia nazionale dei Lincei 1990

Authors and Affiliations

  • Pier Lucio Anelli
    • 1
  • Stefano Banfi
    • 1
  • Fernando Montanari
    • 1
  • Silvio Quici
    • 1
  1. 1.Dipartimento di Chimica Organica e IndustrialeUniversità degli Studi di Milano, Centro CNR Sintesi e Stereochimica di Speciali Sistemi OrganiciMilano

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