Jiao bromination
The Jiao bromination, named after Prof. Ning Jiao from Peking university, is an organic halogenation reaction using DMSO/HBr system.[1] In this reaction, HBr (48% aqueous) provides the bromine source, while dimethyl sulfoxide (DMSO) acts as a mild oxidant. Arene iodination could also be efficiently accomplished using HI aqueous or NH4I.[2]
History
Jiao bromination developed from earlier studies of DMSO-mediated oxidative halogenation (eg. Kornblum oxidation). Megyeri and Keve reported related reactions in 1989,[3] followed by Majetich and co-workers in 1997 and Dai's group in 2014.[4][5] These studies showed that DMSO could promote aromatic bromination under acidic conditions, but often suffered from limited selectivity, substrate scope, or efficiency. In 2015, Jiao and co-workers developed a more practical system using stoichiometric DMSO and hydrogen bromide. DMSO served as a mild oxidant, while the reaction medium was an organic solvent rather than excess DMSO. [2]
Extensions
The DMSO/HBr system has been used for the bromination of arenes and heteroarenes, as well as olefins, alkynes, and ketones.[6] For alkenes, the reaction affords the corresponding dibrominated products. Both terminal and internal alkynes can be converted into the corresponding (E)-dibromoalkenes. In addition, primary, secondary, and tertiary α-bromoketones can be prepared from ketone substrates under Jiao bromination conditions. Beyond the halogenation of (hetero)arenes, the DMSO/HX system also enables the hydrobromination of styrenes in good yields.[7]
Applications
The HBr/DMSO system has been applied not only to the synthesis and modification of natural products, pharmaceutical intermediates, and functional materials, but also to the discovery and development of new reactions. For example, the group of Shi employed the Jiao bromination to access the key brominated intermediate in the total synthesis of quinocarcin.[8] Lou and co-workers modified marine natural products to generate brominated lead compounds with antitumour activity.[9] In 2021, the Chen group reported a redox-divergent strategy for converting dimethyl sulfide, a byproduct of the Jiao bromination reaction involving DMSO, into dihydrothiophenes, thiophenes, and bromothiophenes.[10]
References
- ↑ He, Li-Bowen; Liu, Heng; Chen, Qing-An (2026). "DMSO: A Magic Chemical for Bromination and Chlorination". Chinese Journal of Chemistry. 44 (15): 2593–2605. doi:10.1002/cjoc.70623. ISSN 1614-7065.
- ↑ 2.0 2.1 Song, Song; Sun, Xiang; Li, Xinwei; Yuan, Yizhi; Jiao, Ning (2015-06-19). "Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization". Organic Letters. 17 (12): 2886–2889. doi:10.1021/acs.orglett.5b00932. ISSN 1523-7060. PMID 26010555.
- ↑ Megyeri, Gábor; Keve, Tibor (1989-12-01). "Halogenation of Indole Alkaloids with Halodimethylsulfonium Halogenids and Halodimethylsulfuxonium Halogenids". Synthetic Communications. 19 (20): 3415–3430. doi:10.1080/00397918908052750. ISSN 0039-7911.
- ↑ Majetich, George; Hicks, Rodgers; Reister, Steven (1997-06-27). "Electrophilic Aromatic Bromination Using Bromodimethylsulfonium Bromide Generated in Situ". The Journal of Organic Chemistry. 62 (13): 4321–4326. doi:10.1021/jo970135w. ISSN 0022-3263. PMID 11671753.
- ↑ "Sage Journals: Discover world-class research". Sage Journals. doi:10.3184/174751914X14114780483352. Retrieved 2026-08-25.
- ↑ Song, Song; Li, Xinwei; Sun, Xiang; Yuan, Yizhi; Jiao, Ning (2015). "Efficient bromination of olefins, alkynes, and ketones with dimethyl sulfoxide and hydrobromic acid". Green Chemistry. 17 (6): 3285–3289. doi:10.1039/C5GC00528K. ISSN 1463-9262.
- ↑ Song, Song; Huang, Xiaoqiang; Liang, Yu-Feng; Tang, Conghui; Li, Xinwei; Jiao, Ning (2015). "From simple organobromides or olefins to highly value-added bromohydrins: a versatile performance of dimethyl sulfoxide". Green Chemistry. 17 (5): 2727–2731. doi:10.1039/C5GC00184F. ISSN 1463-9262.
- ↑ Fang, Sheng-Long; Jiang, Meng-Xue; Zhang, Shuo; Wu, Yong-Jie; Shi, Bing-Feng (2019-06-21). "Scalable Formal Synthesis of (−)-Quinocarcin". Organic Letters. 21 (12): 4609–4613. doi:10.1021/acs.orglett.9b01511. ISSN 1523-7060. PMID 31180224.
- ↑ Sun, Bin; Li, Lin; Hu, Qing-wen; Xie, Fei; Zheng, Hong-bo; Niu, Huan-min; Yuan, Hui-qing; Lou, Hong-xiang (2016-10-04). "Design, synthesis and biological evaluation of novel macrocyclic bisbibenzyl analogues as tubulin polymerization inhibitors". European Journal of Medicinal Chemistry. Therapeutic Approaches of Diseases Related to Misfolded Proteins. 121: 484–499. doi:10.1016/j.ejmech.2016.06.007. ISSN 0223-5234.
- ↑ Liu, Heng; He, Gu-Cheng; Zhao, Chao-Yang; Zhang, Xiang-Xin; Ji, Ding-Wei; Hu, Yan-Cheng; Chen, Qing-An (2021). "Redox-Divergent Construction of (Dihydro)thiophenes with DMSO". Angewandte Chemie International Edition. 60 (45): 24284–24291. doi:10.1002/anie.202109026. ISSN 1521-3773.
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