Visible-Light-Accelerated Copper(II)-Catalyzed Regio- and Chemoselective Oxo-Azidation of Vinyl Arenes
Visible-Light-Accelerated Copper(II)-Catalyzed Regio- and Chemoselective Oxo-Azidation of Vinyl Arenes
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DOI：
10.1002/anie.201801678
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发表时间：
2018-07-02
影响因子：
16.6
通讯作者：
Reiser, Oliver
中科院分区：
文献类型：
--
作者：
Hossain, Asik;Vidyasagar, Adiyala;Reiser, Oliver
以三甲基硅氮化物和分子氧为化学计量比氧化剂，实现了乙烯基芳烃的可见光加速氧化叠氮化反应。与基于Ir、Ru或有机染料的光催化剂相比，[Cu(Dap)(2)]Cl或[Cu(Dap)Cl2]对这种转化是独特的，这归因于它们通过配体交换和反弹机制与底物相互作用的能力。铜-II被认为是催化活性物种，在配位叠氮后，它将发生光加速均解生成铜-I和叠氮自由基。该活化原理为(Cu-II-XCuI+X-.)为铜基光催化开辟了新的途径。
The visible-light-accelerated oxo-azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap)(2)]Cl or [Cu(dap)Cl-2] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. Cu-II is proposed as the catalytically active species, which upon coordinating azide will undergo light-accelerated homolysis to form Cu-I and azide radicals. This activation principle (Cu-II-XCuI+X-.) opens up new avenues for copper-based photocatalysis.