Direct C-H Arylation of Aldehydes by Merging Photocatalyzed Hydrogen Atom Transfer with Palladium Catalysis
Direct C-H Arylation of Aldehydes by Merging Photocatalyzed Hydrogen Atom Transfer with Palladium Catalysis
复制标题
光催化氢原子转移与钯催化相结合对醛进行直接 C-H 芳基化
DOI：
10.1021/acscatal.0c02105
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发表时间：
2020-07-17
期刊：
影响因子：
12.9
通讯作者：
Zheng, Chao
中科院分区：
文献类型：
--
作者：
Wang, Lu;Wang, Ting;Zheng, Chao
在此，我们报道将钯催化与氢原子转移（HAT）光催化相结合，能够实现醛的C - H键的直接芳基化和芳烯基化，促进了多种酮的可见光催化构建。发现十钨酸四丁基铵和蒽醌可作为协同的HAT光催化剂。密度泛函理论计算表明存在Pd - 0 - Pd - II - Pd - III - Pd - I - Pd - 0途径，并揭示在KHCO₃存在下，Pd - 0催化剂和光催化剂同时再生。这种再生具有较低的能垒，促进了钯催化循环与光催化循环的高效耦合。本文所报道的工作表明，HAT光催化在钯催化的交叉偶联和C - H官能化反应中的进一步应用具有很大的成功前景。
Herein, we report that merging palladium catalysis with hydrogen atom transfer (HAT) photocatalysis enabled direct arylations and Aralkenylations of aldehyde C-H bonds, facilitating visible light-catalyzed construction of a variety of ketones. Tetrabutylammonium decatungstate and anthraquinone were found to act as synergistic HAT photocatalysts. Density PC isolated yield functional theory calculations suggested a Pd-0-Pd-II-Pd-III-Pd-I-Pd-0 pathway and revealed that regeneration of the Pd-0 catalyst and the photocatalyst occurs simultaneously in the presence of KHCO3. This regeneration features a low energy barrier, promoting efficient coupling of the palladium catalytic cycle with the photocatalytic cycle. The work reported herein suggests great promise for further applications of HAT photocatalysis in palladium-catalyzed cross-coupling and C-H functionalization reactions to be successful.