C-H Xanthylation: A Synthetic Platform for Alkane Functionalization.
C-H Xanthylation: A Synthetic Platform for Alkane Functionalization.
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DOI：
10.1021/jacs.6b09414
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发表时间：
2016-10-26
影响因子：
15
通讯作者：
Alexanian EJ
中科院分区：
文献类型：
--
作者：
Czaplyski WL;Na CG;Alexanian EJ
脂肪族C-H键的分子间功能化为复杂分子的合成和后期衍生化提供了独特的策略，但可进入的化学空间仍然有限。在这里，我们报告了一个转换显着扩大可通过C-H功能化的化学型。C-H黄原胶化以有用的化学产率进行，其中底物作为限制试剂，使用蓝色LED和容易制备的N-黄酰胺。复杂分子的后期官能化以高水平的位点选择性发生，并且在反应中容许各种常见的官能度。这种方法利用了黄原酸酯官能团的多功能性，通过极性和自由基流形来解锁以前在合成中无法实现的广泛的C-H变换。
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 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.