Department of Chemistry, University of Pavia, Viale Taramelli 10, 27100 Pavia, Italy.
Beilstein J Org Chem. 2012;8:967-76. doi: 10.3762/bjoc.8.109. Epub 2012 Jun 28.
We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially chiral binol scaffolds, which incorporate either methoxy or acetoxy functionalities in the 2,2' positions and carboxylic functionalities in the external 3,3' positions, were used as the source of chirality. Two of these binaphthyls are joined through amidation reactions using rigid diaryl amines of differing shapes, to give homochiral tetraamidic macrocycles. The recognition properties of these supramolecular receptors have been analyzed, and the results indicate a modulation of binding affinities towards dicarboxylate anions, with a drastic change of binding mode depending on the steric and electronic features of the functional groups in the 2,2' positions.
我们报告了一种新型的形状保持、光学活性芳酰胺大环的合成与表征，该大环可以通过一锅法得到。使用了手性轴 resolved, axially chiral binol 支架，其在 2,2' 位上含有甲氧基或乙酰氧基官能团，在外部 3,3' 位上含有羧酸官能团，作为手性的来源。这两个双萘酚通过酰胺化反应用不同形状的刚性二芳基胺连接，得到同手性的四酰胺大环。对这些超分子受体的识别性质进行了分析，结果表明对二羧酸根阴离子的结合亲和力有所调节，根据 2,2' 位上官能团的空间和电子特征，结合模式发生了剧烈变化。
