Structure-based analysis and optimization of a highly enantioselective catalyst for the Strecker reaction
Structure-based analysis and optimization of a highly enantioselective catalyst for the Strecker reaction
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DOI：
10.1021/ja027246j
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发表时间：
2002-08-28
影响因子：
15
通讯作者：
Jacobsen, EN
中科院分区：
文献类型：
--
作者：
Vachal, P;Jacobsen, EN
对无金属席夫碱催化的不对称Strecker反应进行了机理研究。使用一系列动力学、结构-活性和NMR实验阐明了催化剂的活性位点、亚胺底物的相关立体异构体和亚胺-催化剂络合物的溶液结构。一个不寻常的桥接之间的相互作用亚胺和尿素的氢的催化剂被确定和支持的计算。基于机理的洞察，催化剂结构的合理优化，导致了一个改进的催化剂的不对称Strecker反应。
A mechanistic investigation of the asymmetric Strecker reaction catalyzed by a metal-free Schiff base catalyst was conducted. The active site of the catalyst, the relevant stereoisomer of the imine substrate, and the solution structure of the imine−catalyst complex were elucidated using a series of kinetics, structure−activity, and NMR experiments. An unusual bridging interaction between the imine and the urea hydrogens of the catalyst was identified and supported by computation. Rational optimization of catalyst structure based on the mechanistic insight led to an improved catalyst for the asymmetric Strecker reaction.