Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323, USA.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6614-6618. doi: 10.1002/anie.201802282. Epub 2018 Apr 14.
The development of synthetic tools to introduce saccharide derivatives into functionally complex molecules is of great interest, particularly in the field of drug discovery. Herein, we report a new route toward highly functionalized, arylated saccharides, which involves nickel-catalyzed cross-coupling of photoredox-generated saccharyl radicals with a range of aryl- and heteroaryl bromides, triggered by an organic photocatalyst. In contrast to existing methods, the mild reaction conditions achieve arylation of saccharide motifs while leaving the anomeric carbon available, thus providing access to a class of arylated glycosides that has been underexplored until now. To demonstrate the potential of this strategy in late-stage functionalization, a variety of structurally complex molecules incorporating saccharide moieties were synthesized.
开发将糖衍生物引入功能复杂分子的合成工具具有重要意义，特别是在药物发现领域。在此，我们报告了一种合成高度功能化芳基化糖的新途径，该途径涉及光还原生成的糖基自由基与一系列芳基和杂芳基溴化物在有机光催化剂的触发下通过镍催化交叉偶联。与现有方法相比，温和的反应条件实现了糖基主题的芳基化，同时使端基碳原子保持可用，从而提供了一类迄今尚未得到充分探索的芳基化糖苷。为了展示该策略在后期功能化中的潜力，合成了多种含有糖基部分的结构复杂的分子。
