Photoinduced site-selective alkenylation of alkanes and aldehydes with aryl alkenes
Photoinduced site-selective alkenylation of alkanes and aldehydes with aryl alkenes
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烷烃和醛与芳基烯烃的光诱导位点选择性烯基化
DOI：
10.1038/s41467-020-15878-6
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发表时间：
2020-04-23
影响因子：
16.6
通讯作者：
Wu, Jie
中科院分区：
文献类型：
--
作者：
Cao, Hui;Kuang, Yulong;Wu, Jie
碳-氢键与烯烃的脱氢烯化反应是一种原子经济和阶梯经济的烯烃合成和分子编辑方法。以C-H底物为限制试剂的烷烃和醛选择性烯化具有重要的合成价值。本文报道了一种光催化方法，在没有任何外部氧化剂的情况下，将烷烃和醛与芳基烯烃直接烯化。各种各样的商品原料和药物化合物在C-H伙伴作为限制试剂的情况下，以有用的产量顺利地烯化。复杂分子的晚期烯烃化发生在具有高水平的位选择性的立体可及和富电子的C-H键。该策略依赖于直接氢原子转移光催化与钴肟介导的析氢交叉偶联的协同组合，这有望以绿色方式激发选择性碳氢官能化的其他观点。碳-氢键的脱氢烯化反应是制备更复杂烯烃的原子经济方法。在这里，作者使用十钨酸盐和钴胺肟催化剂的组合光催化烷烃和脂肪醛脱氢烯化与芳基烯烃。
The dehydrogenative alkenylation of C-H bonds with alkenes represents an atom- and step-economical approach for olefin synthesis and molecular editing. Site-selective alkenylation of alkanes and aldehydes with the C-H substrate as the limiting reagent holds significant synthetic value. We herein report a photocatalytic method for the direct alkenylation of alkanes and aldehydes with aryl alkenes in the absence of any external oxidant. A diverse range of commodity feedstocks and pharmaceutical compounds are smoothly alkenylated in useful yields with the C-H partner as the limiting reagent. The late-stage alkenylation of complex molecules occurs with high levels of site selectivity for sterically accessible and electron-rich C-H bonds. This strategy relies on the synergistic combination of direct hydrogen atom transfer photocatalysis with cobaloxime-mediated hydrogen-evolution cross-coupling, which promises to inspire additional perspectives for selective C-H functionalizations in a green manner. Dehydrogenative alkenylation of C-H bonds is an atom-economical approach to prepare more complex olefins. Here, the authors use a combination of decatungstate and a cobaloxime catalyst for the photocatalytic dehydrogenative alkenylation of alkanes and aliphatic aldehydes with aryl alkenes.