SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps
SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps
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DOI：
10.1021/acs.organomet.6b00371
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发表时间：
2016-07-11
期刊：
影响因子：
2.8
通讯作者：
Cavallo, Luigi
中科院分区：
文献类型：
--
作者：
Falivene, Laura;Credendino, Raffaele;Cavallo, Luigi
开发更高效的催化剂仍然是金属有机化学家的主要目标之一。为了加速实现这一目标，有效的分子描述符和可视化工具可以提供显著的帮助。在这里，我们提供了一个Web应用程序来分析金属络合物的催化口袋，使用地形立体图作为一个通用的和无偏的描述符，适用于每一类催化剂。为了显示我们方法的广泛适用性，我们首先比较了一系列过渡金属配合物的空间构型图，其中包括流行的单、双、四配位配体和三个经典的锆烯。这种比较分析突出了完全不相关的配体之间的相似和不同。然后，我们重点介绍了最近开发的一种Fe(II)催化剂，它对酮和亚胺的不对称转移氢化反应具有很高的活性。最后，我们扩展了这些工具的范围，使酶催化中通过单核对羟基扁桃酸合成酶的三个氨基酸的点突变实现的对映选择性逆转合理化。
Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.