Brown Oliver C, Baguña Torres Julia, Holt Katherine B, Blower Philip J, Went Michael J
University of Kent, School of Physical Sciences, Canterbury CT2 7NH, UK.
Dalton Trans. 2017 Oct 31;46(42):14612-14630. doi: 10.1039/c7dt02008b.
Copper(ii) bis(thiosemicarbazone) derivatives have been used extensively in positron emission tomography (PET) to image hypoxia and blood flow and to radiolabel cells for cell tracking. These applications depend on control of redox potentials and lipophilicity of the bis(thiosemicarbazone) complexes, which can be adjusted by altering peripheral ligand substituents. This paper reports the synthesis of a library of new dissymmetrically substituted bis(thiosemicarbazone) ligands by controlling the condensation reactions between dicarbonyl compounds and 4-substituted-3-thiosemicarbazides or using acetal protection. Copper complexes of the new ligands have been prepared by reaction with copper acetate or via transmetallation of the corresponding zinc complexes, which are convenient precursors for the rapid synthesis of radio-copper complexes. Well-defined structure-activity relationships linking ligand alkylation patterns with redox potential and lipophilicity of the complexes are reported.
铜（II）双（硫代氨基脲）衍生物已广泛应用于正电子发射断层扫描（PET）中，用于成像缺氧和血流情况以及对细胞进行放射性标记以用于细胞追踪。这些应用取决于对双（硫代氨基脲）配合物的氧化还原电位和亲脂性的控制，而这可以通过改变外围配体取代基来进行调节。本文报道了通过控制二羰基化合物与4-取代-3-硫代氨基脲之间的缩合反应或使用缩醛保护来合成一系列新型不对称取代双（硫代氨基脲）配体的方法。通过与醋酸铜反应或通过相应锌配合物的金属转移反应制备了新配体的铜配合物，这些锌配合物是快速合成放射性铜配合物的便利前体。本文还报道了将配体烷基化模式与配合物的氧化还原电位和亲脂性联系起来的明确的构效关系。
