南方科技大学何川团队通过催化对映选择性脱氢硅-氧偶联制备手性硅立体硅氧烷和烷氧基硅烷。 相关研究成果于2021年4月1日发表在国际顶尖学术期刊《美国化学会杂志》。

该文研究了铑催化的三有机取代硅立体硅氧烷和烷氧基硅烷的对映选择性构建。该工艺在二氢硅烷与硅醇或醇之间进行直接的分子间脱氢Si–O偶联，以优异的立体控制获得各种高度官能化的手性硅氧烷和烷氧基硅烷，大大扩展了以硅为中心的手性分子的化学空间。

通过构建CPL活性（圆极化发光）硅立体生成烷氧基硅烷有机小分子，进一步说明了该方法的实用性。光学纯双烷氧基硅烷含有两个硅立体晶中心和三个芘基团，显示出显著的glum值，具有很高的荧光量子效率（glum=0.011，ΦF=0.55），在手性有机光电材料中具有巨大的潜在的应用前景。

附：英文原文

Title: Catalytic Enantioselective Dehydrogenative Si–O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes

Author: Jiefeng Zhu, Shuyou Chen, Chuan He

Issue&Volume: April 1, 2021

Abstract: 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 stereocontrol, 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 glum value with a high fluorescence quantum efficiency (glum = 0.011, ΦF = 0.55), which could have great potential application prospects in chiral organic optoelectronic materials.

DOI: 10.1021/jacs.1c01106

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01106