S. Quici et al., SIMPLE SYNTHETIC MODELS OF CYTOCHROME-P-450 - EFFICIENT CATALYSTS IN HYDROCARBON OXIDATIONS, Gazzetta chimica italiana, 123(11), 1993, pp. 597-612
Metalloporphyrin-catalysed hydrocarbon oxidation is a particularly int
eresting topic both to understand the transient intermediates involved
in the catalytic cycle of natural cytochrome P-450 mono-oxygenases an
d to stimulate the search of new, efficient and selective oxidation ca
talysts to be used for preparative purposes. The aim of this review is
to highlight the efforts of chemists in mimicking cytochrome P-450 en
zymes by means of synthetic models, with the final goal of selectively
oxidising hydrocarbons on a preparative scale, under mild conditions,
using cheap, easy-to-handle and clean oxygen sources. The features of
cytochrome P-450, the synthesis of tetraarylporphyrins and the cataly
tic systems used as models of natural enzymes are briefly surveyed in
the first part of this article. The second part covers the use of simp
le <<self-consistent>> models and of chiral porphyrins capable of ster
eoselective hydrocarbon oxidation. The main problems considered are th
e chemical stability and the efficiency (overall turnover numbers) of
the catalytic systems.