疏水性取代基对水相中脯氨酸催化的Aldol 反应的影响。
Hydrophobic substituent effects on proline catalysis of aldol reactions in water.
机构信息
Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, Pennsylvania 19122, United States.
出版信息
J Org Chem. 2012 May 18;77(10):4784-92. doi: 10.1021/jo300569c. Epub 2012 May 8.
Abstract
Derivatives of 4-hydroxyproline with a series of hydrophobic groups in well-defined orientations have been tested as catalysts for the aldol reactions. All of the modified proline catalysts carry out the intermolecular aldol reaction in water and provide high diastereoselectivity and enantioselectivity. Modified prolines with aromatic groups syn to the carboxylic acid are better catalysts than those with small hydrophobic groups (1a is 43.5 times faster than 1f). Quantum mechanical calculations provide transition structures, TS-1a(water) and TS-1f(water), that support the hypothesis that a stabilizing hydrophobic interaction occurs with 1a.
摘要
一系列具有明确取向的疏水性基团的 4-羟基脯氨酸衍生物已被测试作为醛醇反应的催化剂。所有改性脯氨酸催化剂都在水中进行分子间醛醇反应，并提供高的非对映选择性和对映选择性。与羧酸顺式的芳香族取代基的改性脯氨酸比带有小疏水性基团的改性脯氨酸（1a 比 1f 快 43.5 倍）更好。量子力学计算提供了过渡态结构 TS-1a（水）和 TS-1f（水），支持了与 1a 发生稳定疏水相互作用的假设。
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