Tüzün Ece Zeynep, Pazderová Lucia, Bavol Dmytro, Litecká Miroslava, Hnyk Drahomír, Růžičková Zdeňka, Horáček Ondřej, Kučera Radim, Grűner Bohumír
Institute of Inorganic Chemistry of the Czech Academy of Sciences, 25068 Řež, Czech Republic.
Dpt. of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030/8, 128 43 Prague, Czech Republic.
Inorg Chem. 2024 Oct 28;63(43):20600-20616. doi: 10.1021/acs.inorgchem.4c03257. Epub 2024 Oct 11.
Organic amines are found to be abundant in natural living systems. They also constitute an inestimable family of building blocks available in drug design. Considering the man-made cluster [(1,2-CBH)-3,3'-Co(III)] ion () and its application as an emerging unconventional pharmacophore, the availability of the corresponding amines has been limited and those with amino groups attached directly to carbon atoms have remained unknown. This paper describes the synthesis of compounds containing one or two primary amino groups attached to the carbon atoms of the cobaltacarborane cage that are accessible via the reduction of newly synthesized azides or via the Curtius rearrangement of the corresponding acyl azide. This substitution represents the first members of the series of azides and primary amines with functional groups bound directly to the carbon atoms of the cage. As expected, the absence of the linker along with the presence of the bulky anionic polyhedral ion leads to a significant alteration of the chemical and physicochemical properties. On a broader series of amines of the ion we have thus observed significant differences in the acidity of the amino groups, depending on whether these are attached to the carbon or boron atoms of the cage, or the C-substituted amines contain an aliphatic linker of variable length. The compounds are relevant for potential use as cobalt bis(dicarbollide) structural blocks in medicinal chemistry and material science. Our study includes single-crystal X-ray diffraction (XRD) structures of both amines and a discussion of their stereochemical and structural features.
有机胺在天然生物系统中含量丰富。它们也是药物设计中一类难以估量的构建模块。考虑到人造簇合物[(1,2-CBH)-3,3'-Co(III)]离子（）及其作为一种新兴的非常规药效团的应用，相应胺类的可得性有限，且那些氨基直接连接到碳原子上的胺类仍然未知。本文描述了通过还原新合成的叠氮化物或通过相应酰基叠氮化物的库尔提斯重排来合成含有一个或两个连接到钴碳硼烷笼碳原子上的伯氨基的化合物。这种取代代表了叠氮化物和伯胺系列中首批官能团直接连接到笼碳原子上的成员。正如预期的那样，由于不存在连接基团以及存在庞大的阴离子多面体离子，导致化学和物理化学性质发生显著改变。在更广泛的离子胺系列中，我们因此观察到氨基酸度存在显著差异，这取决于它们是连接到笼的碳原子还是硼原子上，或者碳取代胺是否含有可变长度的脂肪族连接基团。这些化合物在药物化学和材料科学中作为钴双（二碳硼烷）结构单元具有潜在用途。我们的研究包括这两种胺的单晶X射线衍射（XRD）结构以及对它们的立体化学和结构特征的讨论。
