Zhu Jiefeng, Chen Shuyou, He Chuan
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150080, China.
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
J Am Chem Soc. 2021 Apr 14;143(14):5301-5307. doi: 10.1021/jacs.1c01106. Epub 2021 Apr 1.
A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes is developed. This process undergoes a direct intermolecular dehydrogenative Si-O coupling between dihydrosilanes with silanols or alocohols, giving access to a variety of highly functionalized chiral siloxanes and alkoxysilanes in decent yields with excellent control, that significantly expand the chemical space of the silicon-centered chiral molecules. Further utility of this process was illustrated by the construction of CPL-active (circularly polarized luminescence) silicon-stereogenic alkoxysilane small organic molecules. Optically pure bis-alkoxysilane containing two silicon-stereogenic centers and three pyrene groups displayed a remarkable value with a high fluorescence quantum efficiency ( = 0.011, Φ = 0.55), which could have great potential application prospects in chiral organic optoelectronic materials.
开发了一种铑催化的对映选择性构建三有机取代的硅立体异构硅氧烷和烷氧基硅烷的方法。该过程通过二氢硅烷与硅醇或醇之间的直接分子间脱氢硅-氧偶联反应，以良好的产率和出色的控制获得了各种高度官能化的手性硅氧烷和烷氧基硅烷，这显著扩展了以硅为中心的手性分子的化学空间。通过构建具有圆偏振发光（CPL）活性的硅立体异构烷氧基硅烷小分子，展示了该方法的进一步实用性。含有两个硅立体异构中心和三个芘基团的光学纯双烷氧基硅烷显示出显著的 值和高荧光量子效率（ = 0.011，Φ = 0.55），在手性有机光电子材料中具有巨大的潜在应用前景。
