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Rhodium(I)-Catalyzed Enantioselective Activation of Cyclobutanols: Formation of Cyclohexane Derivatives with Quaternary Stereogenic Centers

机译:铑(I)催化的环丁醇的对映选择性活化:带有季立体中心的环己烷衍生物的形成

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摘要

The activation of carbon carbon a bonds is a complementary method to access uncommon and difficult-to-prepare organometallic species. Herein, we describe the activation of tert-cyclobutanols through an enantioselective insertion of a chiral rhodium(I) complex into the C-C sigma bond of the cyclobutane, forming a quaternary stereogenic center and an alkyl-rhodium functionality that initiates ring-closure reactions. This technology provides access to a variety of substituted cyclohexane derivatives with quaternary stereogenic centers. The formation of different product families can be controlled by the employed set of reaction conditions and additives. In general, high yields and excellent enantioselectivities of up to 99% ee are obtained.
机译:碳a碳键的活化是一种补充方法,可用于访问不常见且难以制备的有机金属物种。在本文中,我们描述了通过将手性铑(I)复合物对映选择性插入环丁烷的C-Cσ键,形成季立体中心和烷基铑官能团来引发闭环反应,从而激活叔环丁醇。这项技术使人们可以通过立体立体异构中心获得各种取代的环己烷衍生物。可以通过所采用的一组反应条件和添加剂来控制不同产物家族的形成。通常,可获得高达99%ee的高收率和出色的对映选择性。

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