Mild and Efficient Vicinal Dibromination of Olefins Mediated by Aqueous Ammonium Fluoride

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.

Key words

olefins - dibromination - halogen - N-bromosuccinimide - metal-free

• 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.