Biometal Corrole Active Esters and Their Amino Acid and Peptide Conjugates,European Journal of Inorganic Chemistry

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Biometal Corrole Active Esters and Their Amino Acid and Peptide Conjugates
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-06-26 , DOI: 10.1002/ejic.202000472
Julian Oelmann ₁ , Reece G. Miller ₂ , Dirk Baabe ₁ , Nils Metzler-Nolte ₂ , Martin Bröring ₁

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The synthesis of a series of A₂B‐corroles with 4‐carboxyphenyl substituent is described. The macrocycles are prepared from dipyrromethanes and 4‐formylbenzoic acid under Gryko conditions. Redox active biometal complexes are formed from the corrole carboxylic acids with the metal ions of cobalt, iron, and manganese, but not with copper. From all free corrole bases and metal complexes, the respective active esters are obtained in good yields by condensation with NHS (N‐hydroxysuccinimide) and EDC (1‐ethyl‐3‐dimethylaminopropyl‐carbodiimide). Starting from the active esters of the free corrole bases, the copper corroles are accessible in acceptable yields. Oxidation‐ and spin states of the biometal corroles correspond to those of simple corroles and are confirmed spectroscopically and magnetically. Ethylenediamine is efficiently coupled with the corrole carboxylic acids by EDC, whereby selective two‐fold coupling is observed. For the coupling to N_αBoc‐lysine as well as N_αFmoc‐lysine the use of corrole active esters is advantageous. The metalation of corroles carrying N‐protected lysine side chains turns out to proceed only with loss of most of the material. Here, the coupling of the amino acid building block with the metal corrole active ester proved to be the synthetically more applicable variant. The resulting N_αFmoc‐lysine conjugates of both a free base corrole and a manganese corrole complex are shown to be suitable for use in Merrifield solid phase peptide synthesis.

中文翻译：

生物金属Corrole活性酯及其氨基酸和肽缀合物

描述了一系列带有4-羧基苯基取代基的A ₂ B-corroles的合成。大环由二吡咯甲烷和4-甲酰基苯甲酸在Gryko条件下制备。氧化还原活性生物金属配合物是由铁的羧酸与钴，铁和锰的金属离子形成的，而不是由铜形成的。通过与NHS缩合，可以从所有游离的硬脂碱和金属络合物中以高收率获得相应的活性酯（N-羟基琥珀酰亚胺）和EDC（1-乙基-3-二甲基氨基丙基-碳二亚胺）。从游离的Corrole碱的活性酯开始，可以以可接受的产率获得铜Corroles。生物金属腐蚀物的氧化态和自旋态与简单腐蚀物的态相对应，并通过光谱和磁力证实。乙二胺通过EDC有效地与环氧羧酸偶联，从而观察到选择性的两倍偶联。用于耦合到N _α的Boc-赖氨酸以及如N _α的Fmoc赖氨酸使用corrole活性酯是有利的。携带N的腐蚀金属经保护的赖氨酸侧链仅在损失大部分材料的情况下才能继续进行。在此，氨基酸构件与金属腐蚀活性酯的偶联被证明是合成上更适用的变体。所得到的N- _α都为游离碱corrole和将Fmoc-赖氨酸缀合物锰corrole复杂被示为适合于在Merrifield固相肽合成中使用。

更新日期：2020-08-24

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