An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions

Abstract

A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO₂ and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.

Keywords

amine - carbon dioxide - formamides - formylation - potassium carbonate

• References and Notes

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• 20 General Procedure for the Synthesis of Formamide Derivatives: The catalyst (10.0 mol%) was introduced into a 100-mL autoclave equipped with an overhead stirrer and an automatic temperature control system⁵ⁱ containing amine (1 mmol), PMHS (4.0 mmol) and THF (5.0 mL) at r.t. After sealing and flushing the reactor three times with 10 atm of N₂, followed by the CO₂ to the desired pressure, the reactor was heated and stirred vigorously at 530–600 rpm for 12 h. After completion of the reaction, the reactor was cooled to r.t. and the pressure was carefully released. Basic hydrolysis of the reaction mixture was carried out as previously described.^5h The reaction mixture was then extracted with EtOAc (3 × 10 mL), the combined organic layers were dried over anhyd Na₂SO₄, filtered and evaporated in vacuo. The isolated crude oil product was further purified by column chromatography on 100–200 mesh size silica gel (elution with 20:4 → 10:2 petroleum ether–EtOAc) to provide the corresponding pure compound. The spectroscopic data are consistent with those reported in the literature and in agreement with the assigned structures.²¹ Morpholine-4-carbaldehyde (2a): colorless oil; yield: 99%. ¹H NMR (400 MHz, 30 °C, CDCl₃, TMS): δ = 7.92 (s, 1 H), 3.58–3.52 (m, 4 H), 3.44 (t, J = 4.0 Hz, 2 H), 3.28 (t, J = 4.0 Hz, 2 H). ¹³C NMR (100 MHz, 30 °C, CDCl₃, TMS): δ = 160.81, 67.08, 66.26, 45.67, 40.44. GC–MS (EI): m/z (%) = 115 (100) [M]⁺. Indoline-1-carbaldehyde (2o): brown solid; yield: 78%. ¹H NMR (400 MHz, 30 °C, CDCl₃, TMS): δ (mixture of rotamers) = 8.92 (s, 1 H, major), 8.50 (s, 1 H, minor), 7.24–7.14 (m, 3 H), 7.05–7.01 (m, 1 H), 4.05 (t, J = 8.0 Hz, 2 H), 3.14 (t, J = 8.0 Hz, 2 H). ¹³C NMR (100 MHz, 30 °C, CDCl₃, TMS): δ = 157.58, 140.93, 127.57, 126.06, 125.13, 124.28, 109.38, 44.64, 27.17. GC–MS (EI): m/z (%) = 147 (65) [M]⁺. N-Benzyl-N-methylformamide (2q): colorless oil; yield: 95%. ¹H NMR (400 MHz, CDCl₃, 30 °C, TMS): δ (mixture of rotamers) = 8.26 (s, 1 H, major), 8.13 (s, 1 H, minor), 7.37–7.17 (m, 5 H), 4.50 (s, 2 H, minor), 4.37 (s, 2 H, major), 2.82 (s, 3 H, minor), 2.76 (s, 3 H, major). ¹³C NMR (100 MHz, 30 °C, CDCl₃, TMS): δ (mixture of rotamers) = 162.74 (major), 162.57 (minor), 135.96 (minor), 135.69 (major), 128.88 (major), 128.67 (minor), 128.21 (major), 128.08 (minor), 127.62 (minor), 127.36 (major), 53.47 (major), 47.74 (minor), 34.05 (major), 29.44 (minor). GC–MS (EI): m/z (%) = 149 (100) [M]⁺. N-Methyl-N-phenylformamide (2s): brownish oil; yield: 93%. ¹H NMR (400 MHz, 30 °C, CDCl₃, TMS): δ = 8.39 (s, 1 H), 7.33 (t, J = 8.0 Hz, 2 H), 7.20 (t, J = 8.0 Hz, 1 H), 7.10 (d, J = 4.0 Hz, 2 H), 3.24 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃, 30 °C, TMS): δ (mixture of rotamers) = 162.27 (major), 162.17 (minor), 142.08, 129.55, 128.96, 126.32 (major), 126.16 (minor), 123.53, 122.26, 31.95. GC–MS (EI): m/z (%) = 135 (85) [M]⁺.
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