Jiang Qifeng, Gittens Alexandra F, Wong Sydnee, Siegler Maxime A, Klausen Rebekka S
Department of Chemistry, Johns Hopkins University 3400 N. Charles St Baltimore MD 21218 USA
Chem Sci. 2022 Jun 6;13(25):7587-7593. doi: 10.1039/d2sc01690g. eCollection 2022 Jun 29.
Main group organometallic compounds can exhibit unusual optical properties arising from hybrid σ,π-conjugation. While linear silanes are extensively studied, the shortage of methods for the controlled synthesis of well-defined cyclic materials has precluded the study of cyclic conjugation. Herein we report that Ru-catalyzed addition of cyclosilanes to aryl acetylenes (hydrosilylation) proceeds with high chemoselectivity, regioselectivity, and diastereoselectivity, affording complex organosilanes that absorb visible light. We further show that the hydrosilylation products are useful building blocks towards novel conjugated polymers.
主族有机金属化合物可展现出源自σ、π杂化共轭的异常光学性质。虽然线性硅烷已得到广泛研究，但缺乏用于可控合成结构明确的环状材料的方法阻碍了对环状共轭的研究。在此，我们报道钌催化环硅烷与芳基乙炔的加成反应（硅氢化反应）具有高化学选择性、区域选择性和非对映选择性，可得到吸收可见光的复杂有机硅烷。我们进一步表明，硅氢化反应产物是合成新型共轭聚合物的有用构建单元。
