Chemistry Letters, Vol.42, No.11, 1366-1368, 2013
Intramolecular Oxidative O-Demethylation in a Per-O-methylated beta-Cyclodextrin-Iron Porphyrin Inclusion Complex in Aqueous Solution
The reaction of a supramolecular home enzyme model (methemoCD2), a 1:1 inclusion complex of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinatoiron(III) ((FeTPPS)-T-III) and a per-O-methylated beta-cyclodextrin dimer having a OCH2PyCH2O (PY: pyridin-3,5-diyl) linker (Py2CD), with peroxy acid (m-chloroperbenzoic acid or peracetic acid) caused intramolecular mono- and di-O-demethylations of the OCH3 group(s) of Py2CD. The O-demethylation seemed to proceed through the hydroxylation of a C-H bond of OCH3 by an oxoiron(IV) porphyrin pi-cation radical (O=(FeP center dot+)-P-IV).