A Rational Synthetic Approach to 2,5-Diphenyl-β-silyl Phospholes
A Rational Synthetic Approach to 2,5-Diphenyl-β-silyl Phospholes
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DOI：
10.1002/ejic.201500874
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发表时间：
2016-02-01
影响因子：
2.3
通讯作者：
Pietschnig, Rudolf
中科院分区：
文献类型：
--
作者：
Klintuch, Dieter;Krekic, Kristijan;Pietschnig, Rudolf
系统地获得β-甲硅烷基取代的磷杂环戊烯的报告。合成过程是通过将磷化锂加成到二炔上，并使中间体β-磷杂锂硅烷化。通过遵循这种方法，单和二甲硅烷基化已经完成，并且已经探索了β甲硅烷基磷杂环戊二烯对硫族元素氧化和转化成磷脂的反应性。甲硅烷基单元对磷杂环戊二烯体系的荧光性质有显著影响，导致斯托克斯位移增加和吸收蓝移，发射红移。关键化合物已通过多核NMR光谱、质谱和部分单晶X射线衍射分析进行了表征。
Systematic access to beta-silyl-substituted phospholes is reported. The synthesis proceeds through the addition of lithium phosphanide to a diyne and silylation of the intermediate beta-lithio phosphole. By following this approach, mono and disilylation has been accomplished and the reactivity of the beta silyl phospholes towards oxidation with chalcogens and conversion into phospholides has been explored. The silyl units have a significant impact on the fluorescence properties of the phosphole system, leading to increased Stokes shifts and blueshifted absorption with redshifted emission. The key compounds have been characterized by multinuclear NMR spectroscopy, mass spectrometry, and, in part, by single-crystal X-ray diffraction analysis.