Stereoselectivity in Asymmetric Catalysis: The Case of Ruthenium-Catalyzed Ketone Hydrogenation
Stereoselectivity in Asymmetric Catalysis: The Case of Ruthenium-Catalyzed Ketone Hydrogenation
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DOI：
10.1021/ct500178w
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发表时间：
2014-06-01
影响因子：
5.5
通讯作者：
Norrby, Per-Ola
中科院分区：
文献类型：
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作者：
Lime, Elaine;Lundhohn, Michelle D.;Norrby, Per-Ola
钌催化简单酮的不对称加氢制对映纯醇是广泛应用于精细化工、制药、香料等行业的重要工艺。手性二膦- rucl2 -1,2-二胺配合物是反应的有效催化剂，具有较高的化学选择性和对映选择性。然而，目前还没有发现二膦- rucl2 -1,2-二胺配合物对各种特定底物都具有普适性，可以通过虚拟筛选作为每种底物来促进。为酮类底物寻找最佳配体的过程，必须仔细选择配体作为传统的催化剂库实验筛选的补充。我们利用改进的Q2MM方法生成了钌催化简单酮不对称氢化反应的过渡态力场（TSFF）。建立的TSFF可以预测13种催化体系的对映体选择性，平均无符号误差为2.7 kJ/mol。
The ruthenium-catalyzed asymmetric hydrogenation of simple ketones to generate enantiopure alcohols is an important process widely used in the fine chemical, pharmaceutical, fragrance, and flavor industries. Chiral diphosphine-RuCl2-1,2-diamine complexes are effective catalysts for the reaction giving high chemo- and enantioselectivity. However, no diphosphine-RuCl2-1,2-diamine complex has yet been discovered that is universal for all kinds of specific substrate can be facilitated by using virtual screening as each substrate. The procedure of finding the best ligands for a ketone substrates, and the ligands must be carefully chosen for a complement to the traditional experimental screening of catalyst libraries. We have generated a transition state force field (TSFF) for the ruthenium-catalyzed asymmetric hydrogenation of simple ketones using an improved Q2MM method. The developed TSFF can predict the enantioselectivity for 13 catalytic systems taken from the literature, with a mean unsigned error of 2.7 kJ/mol.