Preparation of dithienylphospholes by 1,1-carboboration.
Preparation of dithienylphospholes by 1,1-carboboration.
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DOI：
10.1002/chem.201403102
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发表时间：
2014-09
期刊：
影响因子：
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通讯作者：
Juri Möbus;A. Galstyan;Andreas Feldmann;C. Daniliuc;R. Fröhlich;C. Strassert;G. Kehr;G. Erker
中科院分区：
文献类型：
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作者：
Juri Möbus;A. Galstyan;Andreas Feldmann;C. Daniliuc;R. Fröhlich;C. Strassert;G. Kehr;G. Erker
在本研究中，1,1-碳硼化反应的范围扩展到混合杂基共轭 π 系统的制备。合成了两种芳基双(炔基)膦起始材料2，其在炔单元处带有两种噻吩异构体，并且在磷原子处带有大的tipp取代基(tipp=2,4,6-三异丙基苯基)。双(噻吩基乙炔基)膦2在温和的反应条件下使用强亲电子B(C6F5)3试剂在双1,1-碳硼化反应序列中转化为相应的2,5-噻吩基取代的3-硼基膦4。随后的 Suzuki-Miyaura 型交叉偶联在一锅法中从磷烷 2 中以高产率产生了相应的 3-苯基磷杂环磷 7。磷光体7被转化为相应的磷光体氧化物8。对衍生物7和8进行了光物理表征。这里给出的结果证明了 1,1-碳硼化反应适用于制备基于磷杂环磷/噻吩的发光系统。
In this study the scope of the 1,1-carboboration reaction was extended to the preparation of mixed heterole-based conjugated π-systems. Two arylbis(alkynyl)phosphane starting materials 2 were synthesized bearing two thiophene isomers at the alkyne units and the bulky tipp-substituent (tipp=2,4,6-triisopropylphenyl) at the phosphorous atom. The bis(thienylethynyl)phosphanes 2 were converted into the corresponding 2,5-thienyl-substituted 3-borylphospholes 4 in a double 1,1-carboboration reaction sequence employing the strongly electrophilic B(C6 F5 )3 reagent under mild reaction conditions. Subsequent Suzuki-Miyaura type cross-coupling yielded the corresponding 3-phenylphospholes 7 in a one-pot procedure from phosphanes 2 in high yields. Phospholes 7 were converted into the respective phosphole oxides 8. A photophysical characterization of derivatives 7 and 8 was carried out. The results presented here demonstrate the suitability of the 1,1-carboboration reaction for the preparation of phosphole-/thiophene-based, light-emitting systems.