CuCl2‐Catalyzed α‐Chloroketonation of Aromatic Alkenes via Visible‐Light‐Induced LMCT

• Published in: Chemistry, an Asian journal Vol. 18; no. 1; pp. e202200954 - n/a
• Main Authors: He, Xing‐Xian, Chang, Huan‐Huan, Zhao, Ying‐Xue, Li, Xiang‐Jie, Liu, Sheng‐An, Zang, Zhong‐Lin, Zhou, Cheng‐He, Cai, Gui‐Xin
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 03.01.2023
• Subjects: Alkenes; aromatic alkenes; Charge transfer; Chemical synthesis; Chemistry; Chlorine; Copper; Copper chloride; CuCl2; Light irradiation; LMCT; photocatalysis; α-chloroketones
• ISSN: 1861-4728; 1861-471X; 1861-471X
• DOI: 10.1002/asia.202200954

Here we report a copper‐catalyzed protocol for the synthesis of α‐chloroketones from aromatic alkenes including electron‐deficient olefins under visible‐light irradiation. Preliminary mechanistic studies show that the peroxo Cu(II) species is the key intermediate and hydroperoxyl (HOO⋅) and chlorine (Cl⋅) radicals can be generated by ligand‐to‐metal charge transfer (LMCT). α‐Chloroketonation of aromatic alkenes based on the homolysis of Cu(II) species with visible light irradiation was described. Photoinduced ligand‐to‐metal charge transfer (LMCT) of copper catalyst can generate hydroperoxyl (HOO⋅) and chlorine (Cl⋅) radicals. A wide scope of the substrates and a great tolerance of functional groups were attained in this transformation.