Anorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44227, Dortmund, Germany.
Current address: Institut für Anorganische Chemie, Universität Regensburg, Germany.
Angew Chem Int Ed Engl. 2017 Jun 26;56(27):7991-7994. doi: 10.1002/anie.201702410. Epub 2017 Jun 6.
Selective cleavage of a silicon-carbon bond in tetraorganosilanes is still a great challenge. A new type of Si-C(sp ) bond cleavage in bench-stable (aminomethyl)silanes with common organolithium reagents as nucleophiles has now been identified. Suitable leaving groups are benzyl, allyl, and phenylthiomethyl groups. A β-donor function and polar solvents are essential for the reaction. Simple switching between α-deprotonation and substitution is possible through slight modifications of the reaction conditions. The stereochemical course of the reaction was elucidated by using a silicon-chiral benzylsilane. The new transformation proceeds stereospecifically with inversion of configuration and can be used for the targeted synthesis of enantiomerically pure tetraorganosilanes, which are otherwise difficult to access. Quantum chemical calculations provided insight into the mechanism of the new substitution.
在四有机硅烷中选择性地切断硅-碳键仍然是一个巨大的挑战。现在已经确定了一种新型的 Si-C(sp ) 键在稳定的（氨甲基）硅烷中与常见的有机锂试剂作为亲核试剂的断裂。合适的离去基团是苄基、烯丙基和苯硫甲基。β-给体功能和极性溶剂对反应是必不可少的。通过稍微改变反应条件，可以在 α-去质子化和取代之间进行简单的切换。通过使用硅手性苄基硅烷，阐明了反应的立体化学过程。新的转化具有构型翻转的立体特异性，可以用于目标合成否则难以获得的对映纯四有机硅烷。量子化学计算提供了对新取代反应机制的深入了解。
