Application of the sila-Friedel-Crafts reaction to the synthesis of π-extended silole derivatives and their properties
Application of the sila-Friedel-Crafts reaction to the synthesis of π-extended silole derivatives and their properties
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DOI：
10.1039/c0dt00136h
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发表时间：
2010-01-01
影响因子：
4
通讯作者：
Kawashima, Takayuki
中科院分区：
文献类型：
--
作者：
Furukawa, Shunsuke;Kobayashi, Junji;Kawashima, Takayuki
分子内Sila-Friedel-Crafts反应是一种构建二苯并噻咯骨架的新方法。该反应在温和的条件下进行，以相对良好的产率提供目标，表明其作为通用合成方法的可用性。该反应可应用于π-延伸的噻咯衍生物如梯形硅芴8和螺型硅杂芴9的合成。此外，利用sila-Friedel-Crafts反应作为多分子内环化实现了二维扩展的噻咯衍生物的合成，包括首次合成了三硅苏曼烯18。trisilasumanene 18的X射线晶体学分析表明，在主要的π-框架的平面性，与sumanene和它的硫类似物，trithiasumanene，轴承碗状结构。在紫外-可见吸收光谱中，与六丁氧基苯并菲22相比，三苯并噻咯18和19的吸收带略微红移。在18和19中的较长波长区域中也观察到弱吸收带，这是由噻咯骨架的sigma*-pi* 共轭引起的。此外，18和19在二氯甲烷中和固体状态下均显示出蓝色荧光。
The intramolecular sila-Friedel-Crafts reaction was developed as a new method for the construction of a dibenzosilole skeleton. This reaction proceeds under mild conditions to afford the target in relatively good yield, indicating its availability as a versatile synthetic method. This reaction can be applied to the synthesis of pi-extended silole derivatives such as ladder-type silafluorene 8 and spiro-type silabifluorene 9. Furthermore, the synthesis of two-dimensionally extended silole derivatives utilizing the sila-Friedel-Crafts reaction as the multiple intramolecular cyclization was achieved, including the first synthesis of trisilasumanene 18. The X-ray crystallographic analysis of trisilasumanene 18 demonstrated the planarity in the main pi-framework, in contrast to sumanene and its sulfur analogue, trithiasumanene, bearing the bowl-shaped structures. In the UV-vis absorption spectra, the absorption bands of triphenylenosiloles 18 and 19 were slightly red-shifted compared to that of hexabutoxytriphenylene 22. The weak absorption bands were also observed in the longer-wavelength region in 18 and 19, which is derived from sigma*-pi* conjugation of the silole skeletons. In addition, 18 and 19 showed the blue fluorescence in dichloromethane and in the solid state.