One-Pot Oxidative Conversion of Alcohols into Nitriles by Using a TEMPO/PhI(OAc)₂/NH₄OAc System

Dedicated to the memory of Professor Serge David

Abstract

A direct conversion of alcohols into nitriles with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), iodosobenzene diacetate, and ammonium acetate as a nitrogen source is reported. This transformation, which proceeds through an oxidation–imination–aldimine oxidation sequence in situ, has been applied to a range of aliphatic, benzylic, heteroaromatic, allylic, and propargyl alcohols. Highly chemoselective ammoxidation of primary alcohols in the presence of secondary alcohols was also achieved.

Key words

alcohols - chemoselectivity - nitriles - oxidation - ­TEMPO

• References and Notes

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• 12 Oxidative Conversion of Alcohols into Nitriles; General Procedure: To a solution of alcohol (1 mmol) in MeCN–H₂O (9:1, 3 mL) were successively added TEMPO (7.8 mg, 5 mol%), NH₄OAc (0.308 g, 4 equiv), and PhI(OAc)₂ (0.708 g, 2.2 equiv). The suspension was stirred at room temperature (progress of the reaction was monitored by TLC) for the reaction time indicated in Table 2. The resultant clear two-phase reaction mixture was concentrated, diluted with H₂O and Et₂O, and the organic layer was dried (Na₂SO₄), filtered, and evaporated under reduced pressure. The residue was purified by flash column chromatography (PE–Et₂O or PE–CH₂Cl₂) to give 2.(Trityloxy)pentanenitrile (2d): Eluent: PE–Et₂O (95:5). Yield: 92%; solid; mp 72–74 °C (hexane). ¹H NMR (300 MHz, C₆D₆): δ = 7.56–7.46 (m, 6 H), 7.22–7.11 (m, 6 H), 7.11–7.02 (m, 3 H), 2.92 (t, J = 6.1 Hz, 2 H), 1.41 (t, J = 7.1 Hz, 2 H), 1.37–1.28 (m, 2 H), 1.17–1.06 (m, 2 H). ¹³C NMR (75 MHz, C₆D₆): δ = 144.7 (3C), 129.0 (6C), 128.1 (6C), 127.3 (3C), 119.3, 86.9, 62.6, 29.0, 22.6, 16.5. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₄H₂₃NNaO: 364.1672; found: 364.1663.5-[(tert-Butyldimethylsilyl)oxy]pentanenitrile (2e): Eluent: PE–Et₂O (9:1); Yield: 97%; liquid. ¹H NMR (300 MHz, C₆D₆): δ = 3.27 (t, J = 5.7 Hz, 2 H), 1.54 (t, J = 6.7 Hz, 2 H), 1.32–1.06 (m, 4 H), 0.91 (m, 9 H), –0.02 (m, 6 H). ¹³C NMR (75 MHz, C₆D₆): δ = 119.4, 62.0, 31.6, 26.1 (3 C), 22.4, 18.4, 16.5, –5.3 (2 C). HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₂₃NNaOSi: 236.1441; found: 236.1435.(Z)-4-(Benzyloxy)but-2-enenitrile (2r): Eluent: PE–Et₂O (4:1). Yield: 92%; liquid. ¹H NMR (300 MHz, C₆D₆): δ = 7.22–7.02 (m, 5 H), 5.82 (dt, J = 11.3, 6.0 Hz, 1 H), 4.56 (dt, J = 11.3, 1.8 Hz, 1 H), 4.10 (s, 2 H), 3.86 (dd, J = 6.0, 1.8 Hz, 2 H). ¹³C NMR (75 MHz, C₆D₆): δ = 150.2, 138.1, 128.6 (2 C), 128.0, 127.97 (2 C), 115.3, 100.3, 72.9, 68.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₁₁NNaO: 196.0733; found: 196.0731.10-Hydroxyundecanenitrile (2t): Eluent: PE–Et₂O (1:2). Yield: 84%; liquid. ¹H NMR (300 MHz, CDCl₃): δ = 3.79–3.64 (m, 1 H), 2.28 (t, J = 7.1 Hz, 2 H), 2.11 (s, 1 H), 1.64–1.53 (m, 2 H), 1.45–1.18 (m, 12 H), 1.12 (d, J = 6.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 119.7, 67.7, 39.0, 29.2, 29.0, 28.44, 28.38, 25.45, 25.1, 23.2, 16.9. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₂₁NNaO: 206.1515; found: 206.1510.10-Oxoundecanenitrile (2t′): Eluent: PE–Et₂O (1:2). Yield 8%; liquid. ¹H NMR (400 MHz, CDCl₃): δ = 2.41 (t, J = 7.4 Hz, 2 H), 2.36–2.28 (m, 2 H), 2.12 (s, 3 H), 1.73–1.12 (m, 12 H). ¹³C NMR (101 MHz, CDCl₃): δ = 209.1, 119.75, 43.6, 29.8, 29.0, 28.9, 28.5 (2 C), 25.3, 23.6, 17.05. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₁₉NNaO: 204.1359; found: 204.1355.3-Hydroxy-2,2,4-trimethylpentanenitrile (2u): Eluent: PE–Et₂O (1.5:1). Yield: 87%; oil. ¹H NMR (300 MHz, CDCl₃): δ = 3.20 (d, J = 3.2 Hz, 1 H), 2.44 (s, 1 H), 2.04–1.9 (m, 1 H), 1.39 (s, 3 H), 1.30 (s, 3 H), 1.02 (s, 3 H), 1.00 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 124.3, 79.9, 37.0, 29.9, 24.7, 23.7, 21.6, 15.4. HRMS (ESI): m/z [M + Na]⁺ calcd for C₈H₁₅NNaO: 164.1046; found: 164.1039.Methyl 2,3-Di-O-benzyl-α-d-glucopyranosiduronitrile (2v): Eluent: PE–Et₂O (2:1). Yield: 77%; glass; [α]_D ²⁰ +76.4 (c 1.3, MeOH). ¹H NMR (300 MHz, CDCl₃): δ = 7.43–7.30 (m, 10 H), 4.93 (d, J = 11.3 Hz, 1 H), 4.79 (d, J = 7.7 Hz, 1 H), 4.75 (d, J = 7.0 Hz, 1 H), 4.64 (d, J = 11.6 Hz, 1 H), 4.60 (d, J = 3.3 Hz, 1 H), 4.36 (d, J = 9.1 Hz, 1 H), 3.74 (t, J = 8.6 Hz, 1 H), 3.67 (t, J = 8.9 Hz, 1 H), 3.48 (dd, J = 3.4, 9 Hz, 1 H), 3.43 (s, 3 H), 3.10 (br s, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 138.0, 137.45, 128.53 (2 C), 128.50 (2 C), 128.1 (1 C), 128.03 (2 C), 127.94 (1 C), 127.91 (2 C), 116.8, 98.8, 79.7, 78.2, 75.45, 73.6, 71.35, 61.6, 56.25. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₁H₂₃NNaO₅: 392.1468; found: 392.1457.