Change of Selectivity in C-H Functionalization Promoted by Nonheme Iron(IV)-oxo Complexes by the Effect of the
Marika Di Berto Mancini1, Andrea Del Gelsomino1, Stefano Di Stefano1
1Dipartimento di Chimica and Istituto CNR per i Sistemi Biologici (ISB-CNR), Sezione Meccanismi di Reazione, c/o Dipartimento di Chimica, Università di Roma "La Sapienza", P.le A. Moro, 5, I-00185 Rome, Italy.
Abstract:
A kinetic analysis of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the iron(IV)-oxo complex [(N4Py)FeIV(O)]2+ and to the phthalimide N-oxyl radical (PINO) has been carried out. The results indicate that a higher activating effect of α-heteroatoms toward the HAT from C-H bonds is observed with the more electrophilic PINO radical. When the N-hydroxy precursor of PINO, N-hydroxyphthalimide (NHPI), is used as a HAT mediator in the oxidation promoted by [(N4Py)FeIV(O)]2+, significant differences in terms of selectivity have been found. Product studies of the competitive oxidations of primary and secondary aliphatic alcohols (1-decanol, cyclopentanol, and cyclohexanol) with alkylaromatics (ethylbenzene and diphenylmethane) demonstrated that it is possible to modify the selectivity of the oxidations promoted by [(N4Py)FeIV(O)]2+ in the presence of NHPI. In fact, alkylaromatic substrates are more reactive in the absence of the mediator while alcohols are preferably oxidized in the presence of NHPI.
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