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首页> 外文期刊>Chemistry: A European journal >Mechanistic Study on Rh-Catalyzed Stereoselective C-C/C-H Activation of tert-Cyclobutanols
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Mechanistic Study on Rh-Catalyzed Stereoselective C-C/C-H Activation of tert-Cyclobutanols

机译：叔丁基环丁醇的Rh催化立体选择性C-C / C-H活化的机理研究

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摘要

A mechanistic study was performed on the Rh-catalyzed stereoselective C-C/C-H activation of tert-cyclobutanols. The present study corroborated the previous proposal that the reaction occurs by metalation, β-C elimination, 1,4- Rh transfer, C=O insertion, and a final catalyst-regeneration step. The rate-determining step was found to be the 1,4-Rh transfer step, whereas the stereoselectivity-determining step did not correspond to any of the aforementioned steps. It was found that both the thermodynamic stability of the product of the β-C elimination and the kinetic feasibility of the 1,4-Rh transfer and C=O insertion steps made important contributions. In other words, three steps (i.e., β-C elimination, 1,4-Rh transfer, and C=O insertion) were found to be important in determining the configurations of the two quaternary stereocenters.
机译：对叔丁基环丁醇的Rh催化的立体选择性C-C / C-H活化进行了机理研究。本研究证实了先前的建议，即该反应通过金属化，β-C消除，1,4- Rh转移，C = O插入和最终的催化剂再生步骤而发生。发现速率确定步骤是1，4-Rh转移步骤，而立体选择性确定步骤不对应于上述任何步骤。发现消除β-C的产物的热力学稳定性以及1，4-Rh转移和C ＝ O插入步骤的动力学可行性都做出了重要贡献。换句话说，发现三个步骤（即，β-C消除，1，4-Rh转移和C ＝ O插入）对于确定两个四元立体中心的构型很重要。

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