关键词: Aniline Biaryl Photoredox XAT

来  源:   DOI:10.1002/anie.202407979

Abstract:
Radical ipso-substitution offers an alternative to organometallic approaches for biaryl synthesis, but usually requires stoichiometric reagents such as tributyltin hydride. Here, we demonstrate that visible light photoredox catalysis can be used for ipso-biaryl synthesis, via a halogen-atom transfer (XAT) regime. Using amide substrates that promote ipso- over unwanted ortho-addition, we demonstrate smooth biaryl formation with no constraint on the electronic character of the migrating arene ring. The photoreaction can be combined in one operation to achieve a formal arylation of the inert aniline C-N bond.
摘要:
自由基ipso取代为联芳基合成提供了有机金属方法的替代方法,但通常需要化学计量试剂如三丁基锡氢化物。这里,我们证明了可见光光氧化还原催化可以用于ipso-biaryl合成,通过卤素原子转移(XAT)制度。使用酰胺底物,促进ipso超过不需要的邻位加成,我们证明了光滑的联芳基形成,对迁移芳烃环的电子特性没有限制。光反应可以在一个操作中组合以实现惰性苯胺C-N键的形式芳基化。
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