A Nickel(II)‐Containing Vitamin B12 Derivative with a Cofactor‐F430‐type π‐System,Angewandte Chemie International Edition

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A Nickel(II)‐Containing Vitamin B12 Derivative with a Cofactor‐F430‐type π‐System
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-11-15 , DOI: 10.1002/anie.201810983
Christopher Brenig ₁ , Lucas Prieto ₁ , René Oetterli ₁ , Felix Zelder ₁

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F430 is a unique enzymatic cofactor in the production and oxidation of methane by strictly anaerobic bacteria. The key enzyme methyl coenzyme M reductase (MCR) contains a hydroporphinoid nickel complex with a characteristic absorption maximum at around 430 nm in its active site. Herein, the three‐step semisynthesis of a hybrid Ni^II‐containing corrinoid that partly resembles F430 in its structural and spectroscopic features from vitamin B₁₂ is presented. A key step of the route is the simultaneous demetalation and ring closure reaction of a 5,6‐secocobalamin to metal‐free 5,6‐dihydroxy‐5,6‐dihydrohydrogenobalamin with cobaltocene and KCN under reductive conditions. Studies on the coordination chemistry of the novel compound support an earlier hypothesis why nature carefully selected a corphin over a corrin ligand in F430 for challenging nickel‐catalyzed biochemical reactions.

中文翻译：

含镍（II）的维生素B12衍生物和辅因子F430型π系统

F430是严格厌氧细菌在甲烷生产和氧化中的独特酶促因子。关键酶甲基辅酶M还原酶（MCR）包含氢卟啉类镍配合物，其活性位点在430 nm附近具有最大吸收特征。在这里，杂化镍^II的类海葵的三步半合成，部分类似于F430，其结构和光谱特征来自于维生素B ₁₂被表达。这条路线的关键步骤是在还原条件下，将5,6-二硫代钴胺与脱钴的同时进行脱金属和闭环反应，生成无金属的5,6-二羟基-5,6-二氢氢代甲蓝素。对这种新型化合物的配位化学的研究支持了一个较早的假设，即自然界为什么会在F430中精心选择一种蛇毒而不是柯林配体来挑战镍催化的生化反应。

更新日期：2018-11-15

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