The β-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 AgNO 2/ NaNO 2 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 β-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-( NO 2)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-( NO 2)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-( NO 2)2 corrolate.

中文翻译：

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铜β-三硝基氯酸盐

尽管大环的对称性降低可能会导致大量可能的区域异构体，但在考罗大环上进行的 β-硝化反应已被证明具有极强的区域选择性。我们最近报道了谨慎使用 AgNO2/ NaNO2作为一种硝化系统，能够以良好的产率获得基于考罗游离碱及其铜络合物的单硝基和二硝基衍生物，证明是一种有效且具有成本效益的方法。在这项工作中，我们使用 TtBuCorrH 详细研究了该方法的范围3作为榜样。氧化剂的进一步增加将硝化作用推至三个 β-吡咯位置的官能化，尽管也观察到伴随的大环分解。应用经过验证的硝化方法，亚硝酸银和亚硝酸钠的含量是氯的 5 倍，得到 2,3,17-( NO2)3- TtBuPCorrCu 为主要产物，产率为 25%，还有痕量的另一种化合物经 X 射线晶体学分析鉴定为 3,8,17-( NO2)3- TtBuPCorrCu 异构体。鉴于这些最近的结果，我们还重新研究了从双取代反应中获得的硝化产物的表征，从而能够鉴定铜 3,8-( NO2)2证实。