Acetic Acid Promoted Direct Iodination of Terminal Alkynes with N-Iodosuccinimide: Efficient Preparation of 1-Iodoalkynes

Abstract

An efficient and highly chemoselective approach for the direct iodination of terminal alkynes using acetic acid as N-iodosuccinimide activated reagent under metal-free conditions has been developed. This facile process tolerates a variety of terminal alkynes and provides the desired products in good to excellent yields (up to 99%).

Key words

terminal alkynes - halogenation - 1-iodoalkynes - carboxylic acids - N-iodosuccinimide

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• 12 Iodination of Terminal Alkynes; General Procedure: To a mixture of terminal alkynes (2.0 mmol), acetic acid (2.6 mmol) and 4 Å MS (200 mg) in MeCN (10 mL) was added N-iodosuccinimide (2.2 mmol) and the resulting mixture was heated at 80 °C for 1.5 h. After completion of the reaction, the reaction was quenched with saturated aqueous sodium thiosulfate and the mixture was extracted with ethyl acetate (10 × 3 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel. (Iodoethynyl)benzene (2aa): Prepared according to the general procedure. Purification by column chromatography (petroleum ether) gave 2aa in 91% yield as a pale-yellow oil. ¹H NMR (CDCl₃, 400 MHz): δ = 7.47–7.44 (m, 2 H), 7.34–7.32 (m, 3 H). ¹³C NMR (CDCl₃, 101 MHz): δ = 132.38, 128.88, 128.32, 123.38, 94.23, 6.74. The overall spectroscopic data are in agreement with assigned structures and consistent with reported data.^8c