State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry , Nankai University , Tianjin 300071 , China.
J Am Chem Soc. 2019 Mar 20;141(11):4579-4583. doi: 10.1021/jacs.9b02127. Epub 2019 Mar 8.
Geminal bis(silanes) are versatile synthetic building blocks owing to their stability and propensity to undergo a variety of transformations. However, the scarcity of catalytic methods for their synthesis limits their structural diversity and thus their utility for further applications. Herein we report a new method for synthesis of geminal bis(silanes) by means of iron-catalyzed dihydrosilylation of alkynes. Iron catalysts were distinctly superior to the other tested catalysts, which clearly demonstrates that novel reactivity can be found by using iron catalysts. This method features 100% atom economy, regiospecificity, mild reaction conditions, and readily available starting materials. Using this method, we prepared a new type of geminal bis(silane) with secondary silane moieties, the Si-H bonds of which can easily undergo various transformations, facilitating the synthetic applications of these compounds. Preliminary mechanistic studies demonstrated that the reaction proceeds via two iron-catalyzed hydrosilylation reactions, the first generating β-( E)-vinylsilanes and the second producing geminal bis(silanes).
偕二硅烷因其稳定性和易于发生多种转化而成为多功能的合成砌块。然而，由于其合成的催化方法稀缺，限制了它们的结构多样性，从而限制了它们在进一步应用中的用途。在此，我们报告了一种通过铁催化炔烃的二氢化硅烷化反应合成偕二硅烷的新方法。铁催化剂明显优于其他测试的催化剂，这清楚地表明，通过使用铁催化剂可以发现新的反应性。该方法具有 100%的原子经济性、区域选择性、温和的反应条件和易得的起始原料。使用这种方法，我们制备了一种新型的偕二硅烷，其中含有仲硅烷部分，其 Si-H 键可以很容易地进行各种转化，从而促进了这些化合物的合成应用。初步的机理研究表明，反应通过两个铁催化的氢化硅烷化反应进行，第一个反应生成 β-（E）-乙烯基硅烷，第二个反应生成偕二硅烷。
