Rhodium(I)-Catalyzed Enantioselective Activation of Cyclobutanols: Formation of Cyclohexane Derivatives with Quaternary Stereogenic Centers
Rhodium(I)-Catalyzed Enantioselective Activation of Cyclobutanols: Formation of Cyclohexane Derivatives with Quaternary Stereogenic Centers
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DOI：
10.1002/chem.200903225
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Cramer, Nicolai
中科院分区：
文献类型：
--
作者：
Seiser, Tobias;Cramer, Nicolai
碳 - 碳单键的活化是获取不常见且难以制备的有机金属物种的一种补充方法。在此，我们描述了通过手性铑（I）配合物对环丁烷的碳 - 碳σ键进行对映选择性插入来活化叔环丁醇，形成一个季碳立体中心和一个引发闭环反应的烷基 - 铑官能团。这项技术提供了获取具有季碳立体中心的多种取代环己烷衍生物的途径。不同产物类型的形成可通过所采用的反应条件和添加剂来控制。一般来说，可获得高产率以及高达99% ee的优异对映选择性。
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.