Photochemical Dehalogenation of Aryl Halides: Importance of Halogen Bonding
- Ayda ElhageAyda ElhageDepartment of Chemistry and Biomolecular Science, Centre for Advanced Materials Research (CAMaR), University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5, CanadaMore by Ayda Elhage
- ,
- Paolo CostaPaolo CostaDepartment of Chemistry and Biomolecular Science, Centre for Advanced Materials Research (CAMaR), University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5, CanadaMore by Paolo Costa
- ,
- Amrah NasimAmrah NasimDepartment of Chemistry and Biomolecular Science, Centre for Advanced Materials Research (CAMaR), University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5, CanadaMore by Amrah Nasim
- ,
- Anabel E. Lanterna*Anabel E. Lanterna*E-mail: [email protected] (A.E.L.).Department of Chemistry and Biomolecular Science, Centre for Advanced Materials Research (CAMaR), University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5, CanadaMore by Anabel E. Lanterna
- , and
- Juan C. Scaiano*Juan C. Scaiano*E-mail: [email protected] (J.C.S.).Department of Chemistry and Biomolecular Science, Centre for Advanced Materials Research (CAMaR), University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5, CanadaMore by Juan C. Scaiano
Abstract
Upon UVA irradiation, aryl halides can undergo dehalogenation in the presence of bases and methanol as a hydrogen donor. This catalyst-free photochemical dehalogenation is furnished through a facile radical chain reaction under mild conditions. The chain reaction follows UVA irradiation of the reaction mixture in a transition-metal-free environment. Mechanistic studies support a chain mechanism in which initiation involves absorption by a methoxide–bromoarene complex facilitated by halogen-bonding interactions. The methoxide–bromine interaction leads to a weakened Br–C bond that is prone to facile cleavage during the initiation and propagation steps.
Cited By
This article is cited by 13 publications.
- Aleksi Sahari, Jukka Puumi, Jere K. Mannisto, Timo Repo. Dual Nickel Photocatalysis for O-Aryl Carbamate Synthesis from Carbon Dioxide. The Journal of Organic Chemistry 2023, 88 (6) , 3822-3829. https://doi.org/10.1021/acs.joc.3c00023
- Velabo Mdluli, Dan Lehnherr, Yu‐hong Lam, Yining Ji, Justin A. Newman, Jungchul Kim. Copper‐Enabled Photo‐Sulfonylation of Aryl Halides Using Alkylsulfinates. Advanced Synthesis & Catalysis 2023, 25 https://doi.org/10.1002/adsc.202300257
- Somayeh Fekri, Yagoub Mansoori, Dolores Esquivel, M. Angeles Navarro. Efficient Hydrodehalogenation of Aryl Halides Catalyzed by Bis(NHC)-Pd(II) Complex Supported on Magnetic Mesoporous Silica. Catalysis Letters 2023, 102 https://doi.org/10.1007/s10562-023-04319-w
- S. R. Hussaini. Radical Reactions. 2023, 597-632. https://doi.org/10.1002/9781119608288.ch14
- Helena F. Piedra, Manuel Plaza. Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp 2 )–S bond forming reactions. Chemical Science 2023, 14 (3) , 650-657. https://doi.org/10.1039/D2SC05556B
- Helena F. Piedra, Carlos Valdés, Manuel Plaza. Shining light on halogen-bonding complexes: a catalyst-free activation mode of carbon–halogen bonds for the generation of carbon-centered radicals. Chemical Science 2023, 141 https://doi.org/10.1039/D3SC01724A
- Xinzhe Tian, Yinggang Guo, Wankai An, Yun-Lai Ren, Yuchen Qin, Caoyuan Niu, Xin Zheng. Coupling photocatalytic water oxidation with reductive transformations of organic molecules. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-33778-9
- Zengyu Zhang, Shiqing Huang, Chen-Yuan Li, Liang-Liang Zhao, Wei Liu, Mohand Melaimi, Guy Bertrand, Xiaoyu Yan. The triplet state of deprotonated mesoionic carbene Breslow intermediates is thermally accessible: Distal difunctionalization of aldehydes. Chem Catalysis 2022, 2 (12) , 3517-3527. https://doi.org/10.1016/j.checat.2022.09.047
- Yinggang Guo, Wankai An, Xinzhe Tian, Lixia Xie, Yun-Lai Ren. Coupling photocatalytic overall water splitting with hydrogenation of organic molecules: a strategy for using water as a hydrogen source and an electron donor to enable hydrogenation. Green Chemistry 2022, 24 (23) , 9211-9219. https://doi.org/10.1039/D2GC02427F
- Liangliang Tong, Xinluo Song, Yuxin Jiang, Bangyao Zhao, Yafeng Li. Efficiently catalytic transfer hydrogenation of aryl and heteroaryl halides by ultrafine palladium nanoparticles confined into UiO-66. International Journal of Hydrogen Energy 2022, 47 (35) , 15753-15763. https://doi.org/10.1016/j.ijhydene.2022.03.066
- Yahuan Liu, Zheng Wang, Ziwei Zhao, Pengxiang Gao, Ning Ma, Qingbin Liu. Efficient base-free hydrodehalogenation of organic halides catalyzed by a well-defined diphosphine-ruthenium(II) complex. Molecular Catalysis 2021, 516 , 111953. https://doi.org/10.1016/j.mcat.2021.111953
- Attila Kunfi, István Jablonkai, Tamás Gazdag, Péter J. Mayer, Péter Pál Kalapos, Krisztina Németh, Tamás Holczbauer, Gábor London. A photoresponsive palladium complex of an azopyridyl-triazole ligand: light-controlled solubility drives catalytic activity in the Suzuki coupling reaction. RSC Advances 2021, 11 (38) , 23419-23429. https://doi.org/10.1039/D1RA03838A
- Margarita I. Bernal-Uruchurtu, Ramón Hernández-Lamoneda. From gas phase to condensed phases: The mutable behavior of the Br2-water interaction. 2021, 235-265. https://doi.org/10.1016/B978-0-12-817586-6.00007-4