Brønsted Acid Catalysed Aerobic Reduction of Olefins by Diimide Generated In Situ from Hydrazine

Abstract

Aerobic reduction of olefins with hydrazine was proven to be efficiently catalysed by readily available Brønsted acids, such as p-tolu­enesulfonic acid monohydrate, providing hydrogenated products in very good yields and chemoselectivity under mild conditions.

Key words

Brønsted acid - diimide - reduction - olefins - hydrazine

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• 14 A mixture of a solution of the olefin (1.0 mmol) in acetonitrile (2 mL) and a 0.05 M stock solution of TsOH·H₂O in acetonitrile (1 mL, 5 mol%) was stirred under an atmosphere of oxygen at 35 °C (for 1a–l) or 70 °C (for 1m–o) for 5 min. To the resulting mixture was then added a solution of NH₂NH₂·H₂O (60 mg, 1.2 mmol) in acetonitrile (1 mL) and the mixture was further stirred at the corresponding temperature and monitored by GC analysis. After complete consumption of the olefin, the reaction was quenched with saturated aqueous NaHCO₃ (3 mL), and Et₂O (15 mL) and H₂O (7 mL) were added. The aqueous layer was removed and the residual organic layer was washed with H₂O (2 × 10 mL) and brine (10 mL), dried over Na₂SO₄, filtered, and concentrated under reduced pressure to give the corresponding hydrogenated product 2a–o. Data for butylbenzene (2a) [CAS Reg. No. 104-51-8]: yield: 127 mg (92%). ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 0.92 (t, J = 7.3 Hz, 3 H, CH₃ ), 1.30–1.42 (m, 2 H, CH₂ ), 1.55–1.65 (m, 2 H, CH₂ ), 2.61 (t, J = 7.8 Hz, 2 H, ArCH₂ ), 7.12–7.31 (m, 5 H, ArH). ¹³C NMR (100 MHz, CDCl₃, 25 °C): δ = 13.9, 22.4, 33.7, 35.7, 125.5, 128.2, 128.4, 142.9. MS (EI): m/z (%) = 134 (26) [M^+·], 105 (8) [C₆H₅CH₂CH₂], 91 (100) [C₆H₅CH₂], 77 (6) [C₆H₅], 65 (16) [C₅H₅], 51 (11) [C₄H₃], 39 (18) [C₃H₃]

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