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Synlett 2018; 29(04): 419-424
DOI: 10.1055/s-0036-1588506
DOI: 10.1055/s-0036-1588506
cluster
Mild and Efficient Vicinal Dibromination of Olefins Mediated by Aqueous Ammonium Fluoride
We thank the Research Grant Council of the Hong Kong Special Administration Region (RGC Ref. No. CUHK14315716) and The Chinese University of Hong Kong Direct Grant (no. 4053203) for financial support. The equipment was partially supported by the Faculty Strategic Fund for Research from the Faculty of Science of the Chinese University of Hong Kong.Further Information
Publication History
Received: 17 May 2017
Accepted after revision: 23 June 2017
Publication Date:
08 August 2017 (online)
Published as part of the Cluster Alkene Halofunctionalization
Abstract
A mild and efficient vicinal dibromination of olefins has been developed by using saturated aqueous ammonium fluoride solution as the promoter. Inexpensive and commercially available N-bromosuccinimide (NBS) was used as the brominating reagent. The corresponding vicinal dibromoalkanes could be obtained in good to excellent yields.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588506.
- Supporting Information
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References and Notes
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- 27 Typical Procedure for the Dibromination of Olefin 1a Using NBS and Aqueous Ammonium Fluoride: To a solution of olefin (1a; 21 mg, 0.202 mmol, 1.0 equiv) in CH2Cl2 (1.0 mL) was added N-bromosuccinimide (78.3 mg, 0.44 mmol, 2.2 equiv) and saturated aqueous ammonium fluoride (0.16 mL) in the absence of light. The resulting mixture was stirred at room temperature and the reaction was monitored by TLC. The reaction was quenched with saturated aqueous Na2S2O3 (5 mL) and extracted with CH2Cl2 (3 × 10 mL). The combined extracts were dried over anhydrous MgSO4 and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography to yield the dibromide 2a (37.1 mg, 70%) as a white solid: 1H NMR (400 MHz, CDCl3): δ = 7.44–7.34 (m, 5 H), 5.16 (dd, J = 10.6, 5.5 Hz, 1 H), 4.09 (dd, J = 10.2, 5.5 Hz, 1 H), 4.03 (t, J = 10.4 Hz, 1 H); 13C NMR (400 MHz, CDCl3): δ = 138.66, 129.25, 128.93, 127.73, 50.98, 35.15; HRMS (EI): m/z [M]+ calcd. for C8H8Br2: 263.8967; found: 263.8972.