Wu Ming, Chen Yi-Wei, Lu Qian, Wang Yong-Bin, Cheng Jun Kee, Yu Peiyuan, Tan Bin
Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China.
J Am Chem Soc. 2023 Sep 20;145(37):20646-20654. doi: 10.1021/jacs.3c07839. Epub 2023 Sep 11.
Chiral organosilanes are valuable chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. As an important strategy for constructing chiral organosilanes, the asymmetric functionalization of the Si-C bond typically relies on transition-metal catalysis. Herein, we present an efficient method for atroposelective synthesis of biaryl siloxane atropisomers via organocatalytic Si-C bond functionalization of dinaphthosiloles with silanol nucleophiles. The reaction proceeds through an asymmetric protonation and simultaneous Si-C bond cleavage/silanolysis sequence in the presence of a newly developed chiral Brønsted acid catalyst. The versatile nature of the Si-C bond streamlines the derivatization of axially chiral products into other functional atropisomers, thereby expanding the applicability of this method.
手性有机硅烷是功能有机材料、不对称催化和药物化学发展中有价值的化学实体。作为构建手性有机硅烷的重要策略，Si-C键的不对称功能化通常依赖于过渡金属催化。在此，我们报道了一种通过二萘基硅烷与硅醇亲核试剂的有机催化Si-C键功能化，对映选择性合成联芳基硅氧烷阻转异构体的有效方法。在新开发的手性布朗斯特酸催化剂存在下，反应通过不对称质子化以及同时进行的Si-C键裂解/硅烷化反应序列进行。Si-C键的多功能性质简化了轴向手性产物向其他功能阻转异构体的衍生化，从而扩大了该方法的适用性。
