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Synlett 2022; 33(02): 182-186
DOI: 10.1055/s-0041-1737293
DOI: 10.1055/s-0041-1737293
letter
One-Pot, Catalyst-Free Synthesis of Nitriles from Aldehydes Using Aminating Reagent MsONH3OTf
This work was supported by National Natural Science Foundation of China (Grant Number 21672086).
Abstract
An eco-friendly protocol to synthesize nitriles from their corresponding aromatic and aliphatic aldehydes in excellent yields has been developed. This is a catalyst-free protocol which employs an aminating reagent (MsONH3OTf) under mild conditions. The hydroxylamine triflic acid salts (MsONH3OTf) acted as the N source for this protocol. Our protocol proved to be easy to perform and presented good functional group tolerance.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1737293.
- Supporting Information
Publikationsverlauf
Eingereicht: 07. Oktober 2021
Angenommen nach Revision: 09. November 2021
Artikel online veröffentlicht:
26. November 2021
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- 18 General Procedure for the Synthesis of Nitriles from AldehydesA solution of aldehyde (0.4 mmol) and MsONH3OTf (0.6 mmol, 1.5 equiv) was mixed in MeCN (4 mL), then the reaction mixture was placed in a preheated oil bath and stirred at 60 °C for the mentioned period while checking the reaction progress (TLC monitored). After completion, the solvent was removed by rotary evaporator, and the crude product was purified by column chromatography on silica gel, using petroleum ether/EtOAc (10:1) as eluent to afford the pure nitriles. The synthesis of both aliphatic and aromatic nitriles obeyed the above workup procedure, except for the compound 2-aminobenzonitrile (2u). After completion, the reaction mixture was extracted with EtOAc and washed with saturated K2CO3 solution, the organic layers were combined and dried with anhydrous Na2SO4. The solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography on silica gel, using petroleum ether/EtOAc (10:1) as eluent to afford 2u.Benzonitrile (2a)Colorless oil (37.1 mg, 90% yield). 1H NMR (400 MHz, CDCl3): δ = 7.66–7.59 (m, 3 H), 7.50–7.46 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 132.6, 132.0, 129.0, 118.7, 112.2. HRMS: m/z calcd for C7H6N [M + H]+: 104.0495; found: 104.0491.2-Aminobenzonitrile (2u)Colorless solid (34.0 mg, 72% yield), mp 45–47 °C. 1H NMR (400 MHz, CDCl3): δ = 7.38–7.30 (m, 2 H), 6.75–6.71(m, 2 H), 4.45 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 149.6, 133.9, 132.2, 117.8, 117.6, 115.1, 95.7. HRMS: m/z calcd for C7H7N2 [M + H]+: 119.0604; found: 119.0601.Heptanenitrile (4a)Colorless oil (32.0 mg, 72% yield). 1H NMR (400 MHz, CDCl3): δ = 2.36–2.33 (m, 2 H), 1.70–1.62 (m, 2 H), 1.49–1.42 (m, 2 H), 1.34–1.28 (m, 4 H), 0.92–0.89 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 119.9, 30.9, 28.3, 25.3, 22.3, 17.1, 13.9 ppm. HRMS: m/z calcd for C7H14N [M + H]+: 112.1121; found: 112.1117.
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