FeCl₂-Catalyzed Aminobromination of Alkenes Using Amides or Sulfonamides and NBS as the Nitrogen and Bromine Sources

Abstract

We have developed a convenient and efficient iron-catalyzed aminobromination of the alkenes using inexpensive FeCl₂ as the catalyst, amides/sulfonamides and NBS as the nitrogen and bromine sources, respectively, under mild conditions.

iron - alkene - aminobromination - amide - sulfonamide - NBS

References and Notes

<A NAME="RW09708ST-1">1</A>

These two authors contributed equally to this work.

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General Experimental Procedure for Aminohalogena-tion of Alkenes
Solid NBS (1.1 mmol, 196 mg) was added to the flask charged with FeCl₂ (0.1 mmol, 13 mg), alkene (1.2 mmol), and amide or sulfonamide (1 mmol) in EtOAc (2 mL). The solution was stirred at r.t. (25 ˚C) or 50 ˚C for about 6 h. The resulting solution was diluted with EtOAc (8 mL) and washed with H₂O and brine. The organic phase was dried over anhyd Na₂SO₄ and concentrated under rotary evaporation, and the residue was purified by column chromatography on silica gel (EtOAc-PE, v/v, 20:1 to 4:1) to provide the pure aminohalogenation product.
(±)- trans -1-( p -Fluorobenzamido)-2-bromocyclopentane (3b)
Yellow oil, yield 84%. ^¹H NMR (300 MHz, CDCl₃): δ = 7.94-7.91 (m, 2 H), 7.09-7.04 (m, 2 H), 5.10 (t, 1 H, J = 5.9 Hz), 4.71 (t, 1 H, J = 7.2 Hz), 2.11-1.92 (m, 2 H), 1.74-1.45 (m, 4 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 162.9, 130.5, 124.1, 115.3, 85.1, 72.0, 34.8, 34.0, 23.3. HRMS: m/z calcd for C₁₂H₁₃BrFNO [M⁺]: 285.0165; found: 285.0171.

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