The Mechanism of the Stetter Reaction - A DFT Study
The Mechanism of the Stetter Reaction - A DFT Study
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DOI：
10.1002/ejoc.200800506
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发表时间：
2008-11-01
影响因子：
2.8
通讯作者：
Yates, Brian F.
中科院分区：
文献类型：
--
作者：
Hawkes, Kirsty J.;Yates, Brian F.
基于Breslow的安息香缩合反应机理，用密度泛函方法研究了一个不对称Stetter反应模型。与协调的安息香缩合反应不同，在Breslow中间体形成后，Stetter反应是一个两步反应过程，其中Breslow中间体和Michael受体的速率决定的C-C偶联先于最终的质子转移。此外，还发现烯醇胺在产物的立体化学中起着重要作用，这种中间体的立体异构体之间的能量差异反映在反应序列的其余部分，因此，对该中间体立体化学的电子和空间控制应该直接提高产品的ee值。((C)Wiley-VCH Verlag GmbH&Co.KGaA，69451，德国温海姆)
On the basis of Breslow's mechanism for benzoin condensation, a model asymmetric Stetter reaction has been investigated using DFT methods. In contrast to the concerted benzoin condensation, after formation of the Breslow intermediate the Stetter reaction is found to lie a two-step process in which the rate-determining C-C coupling of the Breslow intermediate and the Michael acceptor precedes final proton transfer. In addition, the enolamine is found to play a significant role in the stereochemistry of the product, with the energy difference between stereoisomers of this intermediate reflected throughout the remainder of the reaction sequence, Consequently, electronic and steric control of the stereochemistry of this intermediate should directly enhance the ee values of the product. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)