Wan W B, Haley M M
Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, OR 97403-1253, USA.
J Org Chem. 2001 Jun 1;66(11):3893-901. doi: 10.1021/jo010183n.
The synthesis and characterization of star- and trefoil-shaped polyethynyl aromatic structures, which represent model substructures of the all-carbon network graphdiyne, are described. Assembly of these macrocycles is accomplished via 6-fold Sonogashira cross-coupling of hexaiodobenzene using PdP(o-Tol)(3) and CuI as the catalytic system. The development of these modified Sonogashira conditions is detailed. This work has led to the synthesis of a new family of hexakis(phenylbutadiynyl)benzene derivatives (4a-c), the largest of which is the D(3)(h)()-symmetric "trefoil" 2 and is composed of three [18]annulenes fused at a common benzene ring. Attempts at the synthesis of "wheel" 3 are also described. Compound 2 represents the largest fragment of the graphdiyne network to date. UV-vis spectroscopic studies indicate enhanced electron delocalization throughout the extended pi-system.
本文描述了星形和三叶形聚乙炔基芳香结构的合成与表征，这些结构代表了全碳网络石墨二炔的模型子结构。这些大环的组装是通过使用PdP(o-Tol)(3)和CuI作为催化体系，对六碘苯进行六重Sonogashira交叉偶联来完成的。详细介绍了这些改进的Sonogashira条件的开发过程。这项工作导致了一系列新的六（苯基丁二炔基）苯衍生物（4a - c）的合成，其中最大的是具有D(3)(h)对称性的“三叶形”2，它由三个在一个共同苯环处稠合的[18]轮烯组成。还描述了合成“轮形”3的尝试。化合物2代表了迄今为止石墨二炔网络中最大的片段。紫外 - 可见光谱研究表明，在整个扩展的π体系中电子离域增强。
