Huerta Elisa, van Genabeek Bas, Lamers Brigitte A G, Koenigs Marcel M E, Meijer E W, Palmans Anja R A
Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands).
Chemistry. 2015 Feb 23;21(9):3682-90. doi: 10.1002/chem.201405410. Epub 2015 Jan 22.
Supramolecular polymers based on benzene-1,3,5-tricarboxamides (BTAs) functionalized with an L- or D-proline moiety display high catalytic activity towards aldol reactions in water. High turnover frequencies (TOF) of up to 27×10(-4) s(-1) and excellent stereoselectivities (up to 96% de, up to 99% ee) were observed. In addition, the catalyst could be reused and remained active at catalyst loadings and substrate concentrations as low as 0.1 mol % and 50 mM, respectively. A temperature-induced conformational change in the supramolecular polymer triggers the high activity of the catalyst. The supramolecular polymer's helical sense in combination with the configuration of the proline (L- or D-) is responsible for the observed selectivity.
基于用L-或D-脯氨酸部分官能化的苯-1,3,5-三甲酰胺（BTA）的超分子聚合物在水中对羟醛反应显示出高催化活性。观察到高达27×10⁻⁴ s⁻¹的高周转频率（TOF）和优异的立体选择性（高达96%的非对映体过量，高达99%的对映体过量）。此外，该催化剂可以重复使用，并且在低至0.1 mol%的催化剂负载量和50 mM的底物浓度下仍保持活性。超分子聚合物中温度诱导的构象变化引发了催化剂的高活性。超分子聚合物的螺旋方向与脯氨酸（L-或D-）的构型共同决定了观察到的选择性。
