Mechanism of enantioselection in Rh-catalyzed asymmetric hydrogenation. The origin of utmost catalytic performance
Mechanism of enantioselection in Rh-catalyzed asymmetric hydrogenation. The origin of utmost catalytic performance
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DOI：
10.1039/b912440c
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发表时间：
2009-01-01
影响因子：
4.9
通讯作者：
Imamoto, Tsuneo
中科院分区：
文献类型：
--
作者：
Gridnev, Ilya D.;Imamoto, Tsuneo
本文介绍了在最有效的人工催化反应之一——铑催化的不对称氢化反应中对映体选择机理的最新进展。大量的实验和计算数据都与八面体二氢化物配合物中双键的可逆配位发生对映体选择的观点一致，这种选择只有在产生的螯合循环在较少阻碍的象限中形成时才会发生。在其主要特征中，这种产生手性的机制类似于最近发现的酶促反应中发生的三阶段识别过程。
This article describes recent developments in the understanding of the mechanism of enantioselection in one of the most efficient artificial catalytic reactions-Rh-catalyzed asymmetric hydrogenation. Numerous experimental and computational data are consistent with the idea that the enantioselection takes place through the reversible coordination of the double bond in octahedral dihydride complexes, which can happen only if the resulting chelate cycle is formed in the less hindered quadrant. In its main features, this mechanism of generating chirality resembles the recently uncovered three-stage recognition process occurring in enzymatic reactions.