Dual ligand-enabled iron and halogen-containing carboxylate-based photocatalysis for chloro/fluoro-polyhaloalkylation of alkenes

• Published in: Chemical science (Cambridge) 2024-12, Vol.15 (47), p.19936-19943
• Main Authors: Han, Wanru, Zhao, Zhenyan, Jiang, Kui, Lan, Yu, Yu, Xuehan, Jiang, Xiaoyu, Yang, Wei, Wei, Donghui, Li, Shi-Jun, Niu, Linbin
• Format: Article
• Language: English
• Subjects: Acetonitrile; Alkenes; Carboxylates; Chemistry; Iron; Ligands; Photocatalysis; Reagents
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d4sc04038d

Herein, we demonstrate a practical dual ligand-enabled iron photocatalysis paradigm-converting all kinds of halogen-containing carboxylates (C n X m COO − , X: F, Cl, Br) into C n X m radicals for the valuable chloro/fluoro-polyhaloalkylation of non-activated alkenes with easily available trichloroacetonitrile/Selectfluor as the electrophilic halogenation reagent. The modular in situ assembly of the effective iron and C n X m COO − -based light-harvesting species using the two ligands-OMe/CF 3 -substituted bipyridine and acetonitrile/trichloroacetonitrile is evidenced by detailed mechanistic studies. The late-stage modification, low loading amount of iron (TON: 257) and feasible gram-scale synthesis show the utility of this protocol. We thus anticipate that the dual ligand-enabled iron photocatalysis paradigm may facilitate activation and transformation of inert bulk chemicals. Dual ligand-enabled iron photocatalysis for the conversion of all kinds of halogen-containing carboxylates (C n X m COO − , X: F, Cl, Br) to C n X m radicals is disclosed for chloro/fluoro-polyhaloalkylation of non-activated alkenes.