Synthesis and study of C(3)-symmetric hydropyran cyclooligolides with oriented aryl and alcohol appendages at 10 A spacing.
Synthesis and study of C(3)-symmetric hydropyran cyclooligolides with oriented aryl and alcohol appendages at 10 A spacing.
复制标题
具有 10 A 间距的定向芳基和醇附属物的 C(3)-对称氢吡喃环低聚内酯的合成和研究。
DOI：
10.1021/jo991681n
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
Zhao,Q
中科院分区：
文献类型：
--
作者：
Burke,SD;Zhao,Q
介绍了含芳基和羟甲基的c3对称大环的模块化合成方法。这些官能团可以进一步细化，在每个合成的早期安装，并通过模块耦合和大内酯化的迭代序列进行。测定了大环内酯1a−c与碱金属阳离子客体的缔合常数，并根据1h NMR研究（包括Job图）证实了这些大环与Ba2+的三明治型配合物。获得了大环内酯1和1的x射线晶体学数据，并对其进行了详细讨论。这些数据支持大环内酯在结构上定义明确，并预先组织为结合钾阳离子。三（溴乙酰化）大三醇酯43的制备举例说明了适于与肽或碳水化合物残基精化的功能化平台。
Modular syntheses ofC3-symmetric macrocycles with pendant aryl and hydroxymethyl groups are described. These functional groups, amenable to further elaboration, were installed early in each synthesis and carried through an iterative sequence of module coupling and macrolactonization. Association constants for macrolides1a−cwith alkali metal cation guests were determined, and sandwich-type complexes with Ba2+were confirmed for these macrocycles based on1H NMR studies, including Job plots. X-ray crystallographic data for macrolides1aand1cwere obtained and are discussed in detail. These data provide support that the macrolides are structurally well-defined and preorganized for binding the potassium cation. Preparation of the tris(bromoacetylated) macrotriolide43exemplifies a functionalized platform suitable for elaboration with peptide or carbohydrate residues.