Access to Chiral Silicon Centers for Application to Circularly Polarized Luminescence Materials
Access to Chiral Silicon Centers for Application to Circularly Polarized Luminescence Materials
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DOI：
10.1021/acs.joc.7b00583
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发表时间：
2017-06-16
影响因子：
3.6
通讯作者：
Nishihara, Hiroshi
中科院分区：
文献类型：
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作者：
Koga, Shinya;Ueki, Shuhei;Nishihara, Hiroshi
研究了钯-手性亚磷酰胺配合物催化的仲硅烷不对称芳基化反应在低分子量圆偏振发光材料中的应用。不对称芳基化反应为制备季硅中心的关键中间体手性叔硅烷（2-21）提供了一种简便、有效的合成方法。采用分步、一锅法将合适的芳基碘转化为季硅烷（22），具有良好的产率和对映选择性。在本工作合成的化合物中，选择了四种光学纯的叔硅烷（18-21）来研究结构与光学性质之间的关系。光学纯的（S，S）-21显示出最高的CPL发射，具有高荧光量子产率（g（lum）：+0.008，Phi（F）：0.42）。这种简单的分子设计为开发小分子有机CPL染料提供了新的策略。
Asymmetric arylation of secondary silanes catalyzed by a Pd-chiral phosphoramidite complex was developed for application to low-molecular-weight circularly polarized luminescence (CPL) materials. The asymmetric arylation provided a convenient, efficient synthetic method for a variety of chiral tertiary silanes (2-21), which were key intermediates for preparing the quaternary silicon center. A stepwise, one-pot procedure was used to transform the appropriate aryl iodide to the quaternary silane (22) with good yield and enantioselectivity. Among compounds synthesized in this work, four optically pure tertiary silanes (18-21) were selected to investigate the relationship between the structure and optical properties. Optically pure (S,S)-21 displayed the highest CPL emission with a high fluorescence quantum yield (g(lum): +0.008, Phi(F): 0.42). This simple molecular design provides new strategies for developing small organic CPL dyes.