Journal
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
Volume 17, Issue 6-7, Pages 440-446Publisher
WORLD SCIENTIFIC PUBL CO PTE LTD
DOI: 10.1142/S1088424613500120
Keywords
corrole; beta-functionalization; nitration; AgNO2
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Funding
- MIUR Italy (PRIN project) [2009Z9ASCA]
- US National Institutes of Health [CA132861]
- NATIONAL CANCER INSTITUTE [R01CA132861] Funding Source: NIH RePORTER
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The beta-nitration reaction carried out on the corrole macrocycle has been shown to be extremely regioselective, although the reduced symmetry of the macrocycle could potentially lead to a huge number of possible regioisomers. We recently reported that the careful use of AgNO2/NaNO2 as a nitrating system enabled the achievement in good yields of mono- and dinitro-derivatives on both corrole free base and its copper complex, proving to be an efficient and cost-effective method. In this work, we present a detailed study of the scope of this method using TtBuCorrH(3) as a model corrole. A further increase of the oxidant pushes the nitration up to the functionalization of three beta-pyrrolic positions, although concomitant decomposition of the macrocycle is also observed. The application of the proven nitration method with a five-fold excess of both silver and sodium nitrites with respect to corrole, afforded the 2,3,17-(NO2)(3)-TtBuPCorrCu as the main product, in 25% yield, together with traces of another compound identified by X-ray crystallographic analysis as the 3,8,17-(NO2)(3)-TtBuPCorrCu isomer. In light of these recent results, we also reinvestigated the characterization of the nitration products obtained from bis-substitution reactions, allowing among others the identification of the copper 3,8-(NO2)(2) corrolate.
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