Czaplyski William L, Na Christina G, Alexanian Erik J
Department of Chemistry, The University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599, United States.
J Am Chem Soc. 2016 Oct 26;138(42):13854-13857. doi: 10.1021/jacs.6b09414. Epub 2016 Oct 14.
Intermolecular functionalizations of aliphatic C-H bonds offer unique strategies for the synthesis and late-stage derivatization of complex molecules, but the chemical space accessible remains limited. Herein, we report a transformation significantly expanding the chemotypes accessible via C-H functionalization. The C-H xanthylation proceeds in useful chemical yields with the substrate as the limiting reagent using blue LEDs and an easily prepared N-xanthylamide. The late-stage functionalizations of complex molecules occur with high levels of site selectivity, and a variety of common functionality is tolerated in the reaction. This approach capitalizes on the versatility of the xanthate functional group via both polar and radical manifolds to unlock a wide array of C-H transformations previously inaccessible in synthesis.
脂肪族碳氢键的分子间官能团化反应为复杂分子的合成和后期衍生化提供了独特的策略，但可实现的化学空间仍然有限。在此，我们报道了一种能显著扩展通过碳氢键官能团化可实现的化学类型的转化反应。使用蓝色发光二极管和一种易于制备的N-黄原酰胺，以底物作为限量试剂，碳氢键黄原酸化反应能以可观的化学产率进行。复杂分子的后期官能团化反应具有高度的位点选择性，并且反应中能兼容多种常见的官能团。该方法通过极性和自由基两种途径利用黄原酸酯官能团的多功能性，从而实现了一系列以前在合成中无法实现的碳氢键转化反应。
