Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
Organic R&D Department, Nippon Chemical Industrial Co., Ltd., Kameido, Koto-Ku, Tokyo, 136-8515, Japan.
Nat Commun. 2018 Jun 12;9(1):2290. doi: 10.1038/s41467-018-04693-9.
Finding optimal chiral ligands for transition-metal-catalyzed asymmetric reactions using trial-and-error methods is often time-consuming and costly, even if the details of the reaction mechanism are already known. Although modern computational analyses allow the prediction of the stereoselectivity, there are only very few examples for the attempted design of chiral ligands using a computational approach for the improvement of the stereoselectivity. Herein, we report a systematic method for the design of chiral ligands for the enantioselective Markovnikov hydroboration of aliphatic terminal alkenes based on a computational and experimental evaluation sequence. We developed a three-hindered-quadrant P-chirogenic bisphosphine ligand that was designed in accordance with the design guidelines derived from this method, which allowed the Markovnikov hydroboration to proceed with high enantioselectivity (up to 99% ee).
使用试错法寻找过渡金属催化不对称反应的最佳手性配体通常既耗时又昂贵，即使已经了解反应机制的细节。尽管现代计算分析可以预测立体选择性，但只有极少数例子尝试使用计算方法来设计手性配体以提高立体选择性。在此，我们报告了一种基于计算和实验评估序列的设计手性配体用于脂肪族末端烯烃对映选择性 Markovnikov 硼氢化的系统方法。我们开发了一种三受阻象限 P-手性双膦配体，它是根据该方法得出的设计准则设计的，该配体允许 Markovnikov 硼氢化反应具有高对映选择性（高达 99%ee）。
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