Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry
Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry
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与三个笛卡尔轴对齐的官能化芳烃：中心聚茚满化学的扩展
DOI：
10.1351/pac200678040749
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发表时间：
2006
影响因子：
1.8
通讯作者：
D. Kuck
中科院分区：
文献类型：
--
作者：
D. Kuck
中心聚茚烷是一类新颖的三维多环芳烃，其独特的几何特征和结构潜力与芳烃单元的固有正交性有关。因此，该家族中最大的成员，正己烷，一种拓扑上非平面的碳氢化合物，被表示为“笛卡尔六苯”，因为它的六个苯单元中的每一个都延伸到笛卡尔空间的六个方向之一。这一特征是根据正己烷和正己烷家族的两个较低成员，即母体三苯并三醌的x射线晶体结构来讨论的。本文报道了近年来在多功能化和扩展中心聚吲哚烷翼方面的研究进展，包括几种高效的六重和八重C-C交叉偶联反应。介绍了一些特殊的中心聚茚衍生物，如第一个十二倍功能化的中心己烷和在其分子外围具有三个相互正交的邻菲罗啉基团的三苯并三醌。本文概述了进一步扩展三苯并三醌和烯丙烯烯的芳烃外围，最终使石墨岩屑具有中心碗状或鞍状中心的挑战，以及由八个共价结合的三苯并三醌单元组成的“巨型”纳米立方体的假设生成。沿着这条路线，我们最近首次发现了一种相关的固态超分子立方体，它含有8个具有相同绝对构型的特定三溴三硝基三苯并三醌分子。
The unique geometrical features and structural potential of the centropolyindanes, a complete family of novel, 3D polycyclic aromatic hydrocarbons, are discussed with respect to the inherent orthogonality of their arene units. Thus, the largest member of the family, centrohexaindane, a topologically nonplanar hydrocarbon, is presented as a "Cartesian hexabenzene", because each of its six benzene units is stretched into one of the six directions of the Cartesian space. This feature is discussed on the basis of the X-ray crystal structures of centrohexaindane and two lower members of the centropolyindane family, viz. the parent tribenzotriquinacenes. Recent progress in multiple functionalization and extension of the indane wings of selected centropolyindanes is reported, including several highly efficient six- and eight-fold C-C cross-coupling reactions. Some particular centropolyindane derivatives are presented, such as the first twelve-fold functionalized centrohexaindane and a tribenzotriquinacene bearing three mutually orthogonal phenanthroline groupings at its molecular periphery. Challenges to further extend the arene peripheries of the tribenzotriquinacenes and fenestrindanes to give, eventually, graphite cuttings bearing a central bowl- or saddle-shaped center are outlined, as is the hypothetical generation of a "giant" nanocube consisting of eight covalently bound tribenzotriquinacene units. Along these lines, our recent discovery of a related, solid-state supramolecular cube, containing eight molecules of a particular tribromotrinitrotribenzotriquinacene of the same absolute configuration, is presented for the first time.