Chiral diaminopyrrolic receptors for selective recognition of mannosides, part 1: design, synthesis, and affinities of second-generation tripodal receptors.
Chiral diaminopyrrolic receptors for selective recognition of mannosides, part 1: design, synthesis, and affinities of second-generation tripodal receptors.
复制标题
用于选择性识别甘露糖苷的手性二氨基吡咯受体，第 1 部分：第二代三足受体的设计、合成和亲和力。
作者：
C. Nativi;Oscar Francesconi;Gabriele Gabrielli;A. Vacca;S. Roelens
描述了用于识别碳水化合物的新一代手性三脚架受体，其特征在于反式-1，2-二氨基环己烷作为关键结构元件，以及它们对一组生物相关单糖的糖苷的识别特性。与我们小组之前报道的母体氨基吡咯受体相比，在吡咯三脚架结构中引入螯合二氨基单元显着增强了它们的结合能力。此外，结构的手性对亲和力以及选择性有明显的影响，显示出高的对映体区分水平。这些第二代二氨基吡咯三足受体对其他单糖中的甘露糖具有高度选择性，该家族的两个成员分别对α和β端基异构体具有选择性。在乙腈中测得的亲和力，β甘露糖苷的（S）-7为83 μM，α甘露糖苷的（R）-5为127 μM，使其成为迄今为止报道的甘露糖苷的最有效合成受体。亲和力评估需要BC（0）（50）参数的进一步发展，BC（0）（50）参数是一种先前开发的结合描述符，其最终形式现已扩展为包括任何化学计量的复合物，没有任何限制，因此通常可以用于对来自非均质系统的亲和力数据进行排名。
A new generation of chiral tripodal receptors for recognition of carbohydrates, featuring trans-1,2-diaminocyclohexane as a key structural element, and their recognition properties toward a set of glycosides of biologically relevant monosaccharides is described. The introduction of a chelating diamino unit into the pyrrolic tripodal architecture markedly enhanced their binding abilities compared with the parent aminopyrrolic receptors previously reported by our group. In addition, the chirality of the structure had a clear impact on affinities, as well as on selectivities, displaying high enantiodiscrimination levels. These second-generation diaminopyrrolic tripodal receptors are highly selective for mannose among other monosaccharides, with two members of the family being selective for the α and the β anomers respectively. The measured affinities in acetonitrile, 83 μM of (S)-7 for the β mannoside and 127 μM of (R)-5 for the α mannoside, make them the most effective synthetic receptors for mannosides reported to date. The affinity assessment required a further evolution of the BC(0)(50) parameter, a previously developed binding descriptor, which in its ultimate formulation has now been extended to include, with no restrictions, complexes of any stoichiometry, and can thus be generally employed to rank affinity data from heterogeneous systems on a common scale.