JOURNAL 3477
Organic Communications
Year: 2025 Issue: 2 April-June
p.100 - 108
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GRAPHICAL ABSTRACT
ABSTRACT
meso-Tetraarylporphyrin chelates are easily available from parent porphyrins. Their reactions with nitric acid (yellow fuming HNO3, d = 1.52), under optimized conditions in CHCl3 at room temperature, can be carried out selectively, thus giving mainly β,β,β-trinitro-substituted moieties (usually two or three isomers of the above complexes). These intermediates (Cu2+-derivatives; obtained in overall yields of up to 38%), upon the reaction with carbanions bearing a leaving group X at the reactive centre afforded the target products, the ones of vicarious nucleophilic substitution of hydrogen (VNS). This approach allows the synthesis of porphyrin derivatives exhaustively β-substituted in three pyrrole rings (in yields of up to 69%), starting from a simple meso-tetraarylporphyrin complexes. The above two-steps procedure including very attractive VNS reaction gives hydrophilic or amphiphilic moieties that seem to be potential agents in anticancer photodynamic therapy (PDT), practically unavailable by alternative methods.
KEYWORDS- porphyrin complexes
- β-derivatization
- carbanions
- vicarious nucleophilic substitution
- nitro group
- photodynamic therapy
SUPPORTING INFORMATION
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