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CC BY-ND-NC 4.0 · SynOpen 2017; 01(01): 0011-0014
DOI: 10.1055/s-0036-1588790
DOI: 10.1055/s-0036-1588790
letter
Brønsted Acid Catalysed Aerobic Reduction of Olefins by Diimide Generated In Situ from Hydrazine
Further Information
Publication History
Received: 02 March 2017
Accepted after revision: 23 March 2017
Publication Date:
13 April 2017 (online)
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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.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588790.
- Supporting Information
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References and Notes
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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]
For reviews on aerobic reduction with diimide, see:
For pK a values of Brønsted acids, see: