Seliger Jan, Oestreich Martin
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
Angew Chem Int Ed Engl. 2021 Jan 4;60(1):247-251. doi: 10.1002/anie.202010484. Epub 2020 Oct 27.
A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.
报道了一种非酶催化的脂肪族和环状苄醇的动态动力学拆分方法。该方法将快速的过渡金属催化的醇消旋化与对映选择性铜氢催化的醇与硅烷的脱氢硅氧偶联相结合。催化过程相互正交，消旋化催化剂不会促进任何背景反应，如硅醚的消旋化及其非选择性形成。常用的钌半夹心配合物不合适，但双功能钌钳形配合物能完美实现这一目的。由此，外消旋醇混合物的对映选择性硅烷化反应能够以高产率和良好的对映选择性实现。
