Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Innovation Center, Merck KGaA, Frankfurter Straße 250, 64293 Darmstadt, Germany.
J Am Chem Soc. 2022 Jun 15;144(23):10156-10161. doi: 10.1021/jacs.2c04261. Epub 2022 Jun 1.
Functionalized enantiopure organosilanes are important building blocks with applications in various fields of chemistry; nevertheless, asymmetric synthetic methods for their preparation are rare. Here we report the first organocatalytic enantioselective synthesis of tertiary silyl ethers possessing "central chirality" on silicon. The reaction proceeds via a desymmetrizing carbon-carbon bond forming silicon-hydrogen exchange reaction of symmetrical bis(methallyl)silanes with phenols using newly developed imidodiphosphorimidate (IDPi) catalysts. A variety of enantiopure silyl ethers was obtained in high yields with good chemo- and enantioselectivities and could be readily derivatized to several useful chiral silicon compounds, leveraging the olefin functionality and the leaving group nature of the phenoxy substituent.
功能化的手性纯有机硅烷是重要的构建块，在化学的各个领域都有应用；然而，其不对称合成方法却很少见。在这里，我们报告了首例通过有机催化对具有“中心手性”的硅的叔硅醚的对映选择性合成。该反应通过新开发的亚膦酰二咪唑（IDPi）催化剂进行对称双（甲代烯丙基）硅烷与酚的去对称化碳-碳键形成硅-氢键交换反应来进行。通过利用烯烃官能团和苯氧基取代基的离去基团性质，多种对映体纯的硅醚以高收率、良好的化学选择性和对映选择性得到，并可轻易地衍生为几种有用的手性硅化合物。
