Photooxidation of
copper(III) 5,6-dimethoxyphenathriporphyrin and
copper(III) 5,6-dioxophenanthriporphyrin, which contain phenanthrene
or dioxophenathrene moieties built into the macrocyclic frameworks,
resulted in the regioselective cleavage that afforded organometallic
copper(III) complexes of open-chain phenanthribilinone-type acyclic
ligands terminated by carbonyl groups. The copper(III) coordinates
two carbon atoms of phenantherene (dioxophenanthrene) and two nitrogen
atoms of pyrrole and pyrrolone units, preserving the donor sets of
the paternal complexes. The primary dioxygen attack is located at
the meso carbon atom adjacent to the phenanthrene
moiety. Demetalation of copper(III) 21-benzoyl-phenanthribilin-1-one
and copper(III) 21-benzoyl-dioxophenanthribilin-1-one yielded mainly
two diastereomers [15Z
, 20E
] and [15Z
, 20Z
], which differ in the configurations
at two Cα–C
meso
double bonds. The regioselectivity of the cleavage, detected in
the course of experimental studies, has been substantiated by DFT
investigations. The regioselective cleavage of 5,6-dimethoxyphenanthriporphyrin
in reaction with basic iron(III) acetate was detected, providing the
synthetically efficient methodology to produce 21-benzoyl-dioxophenanthribilin-1-one.
A rational synthesis using carba analogues of tripyrrane and 1,3-bis(arylhydroxymethyl)furan as synthons resulted in the formation of 21-carba-23-oxaporphyrin and 21-carba-23-oxachlorin.The molecular design preserves all essential virtues of 21-oxaporphyrin architecture allowing...
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