Benzyltrimethylsilanes react with iodosylbenzene in the presence of either iron(III) or manganese(III) tetrakis(pentafluorophenyl)porphyrin (TFPPM, with M = Fe, Mn) to give alpha-hydroxybenzyltrimethylsilanes, which are then rapidly converted into the corresponding benzaldehydes in the reaction medium. In these reactions the active species is the metal-oxo complex, TFPPM(V)=O, formed by iodosylbenzene and TFPPM. A relative reactivity study for a series of ring substituted benzyltrimethylsilanes has shown that when M = Fe, the reaction is quite selective (rho = -1.85), with the m-MeO substituent exhibiting a much higher reactivity than expected. When M = Mn, a lower rho value (-1.15) is observed and no anomalous reactivity is found with the m-MeO group. These result suggest that the side-chain hydroxylation of benzyltrimethylsilane by TFPPMn(V)=O occurs by the well known hydrogen atom transfer mechanism. For the corresponding reactions induced by TFPPFe(V)=O a coupled proton/electron transfer mechanism, which might involve the formation of a charge-transfer complex, seems more likely.

SIDE-CHAIN OXIDATION OF BENZYLTRIMETHYLSILANES BY IODOSYLBENZENE IN THE PRESENCE OF IRON AND MANGANESE PORPHYRINS / Enrico, Baciocchi; Lanzalunga, Osvaldo. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 49:33(1993), pp. 7267-7276. [10.1016/s0040-4020(01)87204-5]

SIDE-CHAIN OXIDATION OF BENZYLTRIMETHYLSILANES BY IODOSYLBENZENE IN THE PRESENCE OF IRON AND MANGANESE PORPHYRINS

LANZALUNGA, Osvaldo
1993

Abstract

Benzyltrimethylsilanes react with iodosylbenzene in the presence of either iron(III) or manganese(III) tetrakis(pentafluorophenyl)porphyrin (TFPPM, with M = Fe, Mn) to give alpha-hydroxybenzyltrimethylsilanes, which are then rapidly converted into the corresponding benzaldehydes in the reaction medium. In these reactions the active species is the metal-oxo complex, TFPPM(V)=O, formed by iodosylbenzene and TFPPM. A relative reactivity study for a series of ring substituted benzyltrimethylsilanes has shown that when M = Fe, the reaction is quite selective (rho = -1.85), with the m-MeO substituent exhibiting a much higher reactivity than expected. When M = Mn, a lower rho value (-1.15) is observed and no anomalous reactivity is found with the m-MeO group. These result suggest that the side-chain hydroxylation of benzyltrimethylsilane by TFPPMn(V)=O occurs by the well known hydrogen atom transfer mechanism. For the corresponding reactions induced by TFPPFe(V)=O a coupled proton/electron transfer mechanism, which might involve the formation of a charge-transfer complex, seems more likely.
1993
01 Pubblicazione su rivista::01a Articolo in rivista
SIDE-CHAIN OXIDATION OF BENZYLTRIMETHYLSILANES BY IODOSYLBENZENE IN THE PRESENCE OF IRON AND MANGANESE PORPHYRINS / Enrico, Baciocchi; Lanzalunga, Osvaldo. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 49:33(1993), pp. 7267-7276. [10.1016/s0040-4020(01)87204-5]
File allegati a questo prodotto
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/458822
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 12
  • ???jsp.display-item.citation.isi??? 11
social impact