Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USA.
Department of Chemistry, Yale University, New Haven, CT 06520, USA.
Science. 2023 May 19;380(6646):706-712. doi: 10.1126/science.adf6177. Epub 2023 May 18.
Catalytic enantioselective methods that are generally applicable to a broad range of substrates are rare. We report a strategy for the oxidative desymmetrization of -diols predicated on a nontraditional catalyst optimization protocol by using a panel of screening substrates rather than a singular model substrate. Critical to this approach was rational modulation of a peptide sequence in the catalyst incorporating a distinct aminoxyl-based active residue. A general catalyst emerged, providing high selectivity in the delivery of enantioenriched lactones across a broad range of diols, while also achieving up to ~100,000 turnovers.
催化对映选择性方法通常适用于广泛的底物，但很少见。我们报告了一种基于非传统催化剂优化方案的 -二醇不对称氧化策略，该方案使用了一系列筛选底物，而不是单一的模型底物。这种方法的关键是在催化剂中合理调节肽序列，其中包含一个独特的基于氨氧基的活性残基。出现了一种通用催化剂，在提供广泛的二醇的对映体富集内酯方面具有高选择性，同时还实现了高达约 100,000 个周转率。
