School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
J Am Chem Soc. 2017 Mar 29;139(12):4346-4349. doi: 10.1021/jacs.7b01412. Epub 2017 Mar 17.
Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calculations indicate that the key determining factor for the selectivity is the presence or absence of a cation-n interaction between the cation in the acylated catalyst and an appropriate lone pair in the substrate. DFT calculations also provided a predictive model for site-selectivity and this model is validated by various substrates.
在碳水化合物中对羟基进行选择性功能化是化学领域长期存在的挑战之一。现在，我们可以使用一对手性催化剂，有系统和可预测地对吡喃糖中最常见的反-1,2-二醇进行区分。密度泛函理论（DFT）计算表明，选择性的关键决定因素是酰化催化剂中的阳离子与底物中合适的孤对之间是否存在阳离子-π相互作用。DFT 计算还为位点选择性提供了一个预测模型，该模型通过各种底物得到验证。
