Catalytic enantioselective methods that are generally applicable to a broad range of substrates are rare. We report a strategy for the oxidative desymmetrization of meso -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.

中文翻译：

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对映选择性氨氧基自由基催化的通用性优化


通常适用于多种底物的催化对映选择性方法很少见。我们报告了一种氧化去对称化策略细观-二醇基于非传统催化剂优化方案，通过使用一组筛选底物而不是单一模型底物。这种方法的关键是在催化剂中合理调节肽序列，并结合独特的基于氨氧基的活性残基。一种通用催化剂的出现，为多种二醇提供对映体富集的内酯的高选择性，同时还实现了高达约 100,000 次的转换。