We have recently reported the strong and confined, chiral acid-catalyzed asymmetric “silicon−hydrogen exchange reaction”. One aspect of this transformation is that it enables access to enantiopure enol silanes in a tautomerizing σ-bond metathesis, via deprotosilylation of ketones with allyl silanes as the silicon source. However, until today, this reaction has not been applied to racemic, 2-substituted, cyclic ketones. We show here that these important substrates readily undergo a highly enantioselective kinetic resolution furnishing the corresponding kinetically preferred enol silanes. Mechanistic studies suggest the fascinating possibility of advancing the process to a dynamic kinetic resolution.

中文翻译：

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硅氢交换反应：2-取代环酮的催化动力学拆分

我们最近报道了强且受限的手性酸催化的不对称“硅氢交换反应”。这种转变的一个方面是，它可以通过使用烯丙基硅烷作为硅源对酮进行脱甲硅烷基化，在互变异构化 σ 键复分解中获得对映纯烯醇硅烷。然而，直到今天，该反应还没有应用于外消旋的、2-取代的环酮。我们在这里表明，这些重要的底物很容易经历高度对映选择性动力学拆分，提供相应的动力学优选烯醇硅烷。机械研究表明将过程推进到动态动力学分辨率的迷人可能性。