Photoredox One-Pot Synthesis of 3,4-Dihydroquinolin-2(1H)-ones

Abstract

A photoredox one-pot strategy for efficient accessing 3,4-dihydroquinolin-2(1H)-ones from anilines, oxalyl chloride, and electron-deficient alkenes is disclosed. The new approach features excellent synthetic efficiency, readily available starting materials, and simple operations. It is compatible with a variety of anilines and electron-deficient alkenes. A broad array of 3,4-dihydroquinolin-2(1H)-ones were prepared.

Key words

3,4-dihydroquinolin-2(1H)-one - photoredox catalysis - one-pot synthesis - efficient synthesis - oxalyl chloride

Publication History

Received: 22 January 2022

Accepted after revision: 16 February 2022

Article published online:
08 March 2022

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• 12 General Procedure for Photoredox One-Pot Synthesis of 3,4-Dihydroquinolin-2(1H)-ones 8a–t To a dry 20 mL reaction vial equipped with a stir bar was charged with CH₂Cl₂ (2 mL) and oxalyl chloride (3 mmol, 10 equiv), then a solution of anilines (0.3 mmol, 1.0 equiv) in CH₂Cl₂ (2 mL) was added quickly at room temperature. After stirring at the same temperature for 1 h, H₂O (2 mL) was added to the mixture, followed by Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆ (2 mol%), K₂CO₃ (1.5 mmol, 5 equiv), and alkenes (0.9 mmol, 3.0 equiv). The vial was covered and bubbled with nitrogen for 5 min. After irradiated with 36 W blue LEDs for 36 h, the mixture was then diluted with EtOAc (40 mL) and H₂O (5 mL), and the organic layer was recovered, washed with brine, dried over Na₂SO₄, filtrated, concentrated under reduced pressure, and purified with column chromatography to afford 3,4-dihydroquinolin-2(1H)-ones 8a–t.
• 13 1-Benzyl-6-methyl-4-(phenylsulfonyl)-3,4-dihydroquinolin-2(1H)-one (8o) Pale yellow solid; yield 38% (44.7 mg); R_f = 0.14 (25% EtOAc–PE); mp 161–163 °C. IR (film): 2929, 1673, 1509, 1447, 1377, 1308, 1265, 1147, 815 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.70–7.64 (m, 3 H), 7.53–7.49 (m, 2 H), 7.32–7.28 (m, 2 H), 7.25–7.22 (m, 1 H), 7.17–7.13 (m, 3 H), 7.05 (dd, J = 8.4, 1.6 Hz, 1 H), 6.63 (d, J = 8.4 Hz, 1 H), 5.10 (d, J = 16.4 Hz, 1 H), 4.36 (d, J = 7.2 Hz, 1 H), 4.02 (d, J = 16.0 Hz, 1 H), 3.48 (d, J = 17.6 Hz, 1 H), 3.19 (dd, J = 17.6, 7.6 Hz, 1 H), 2.30 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 165.3, 138.2, 136.4, 136.0, 134.2, 132.9, 132.2, 131.2, 129.6 (2×), 128.8 (2×), 128.7 (2×), 127.1, 126.1 (2×), 115.9, 115.7, 63.1, 46.5, 31.9, 20.4. GC–MS: m/z (%) = 91 (100), 249 (95) [M – HSO₂Ph]⁺. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₂₃H₂₂NO₃S: 392.1315; found: 392.1316.
• 14 1-Benzyl-6-methyl-4-propionyl-3,4-dihydroquinolin-2(1H)-one (8p) Pale yellow solid; yield 52% (48.1 mg). R_f = 0.17 (25% EtOAc–PE), mp 118–120 °C. IR (film): 2924, 2854, 1711, 1672, 1505, 1375, 1095, 1030, 803 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.31–7.28 (m, 4 H), 7.24–7.19 (m, 3 H), 7.10 (d, J = 1.6 Hz, 1 H), 6.97 (dd, J = 8.4, 1.2 Hz, 1 H), 6.81 (d, J = 8.4 Hz, 1 H), 5.21 and 5.11 (AB q, J = 16.4, 16.0 Hz, 2 H), 3.85 (dd, J = 6.0, 2.8 Hz, 1 H), 3.16 (dd, J = 16.0, 2.8 Hz, 1 H), 2.84 (dd, J = 16.0, 6.0 Hz, 1 H), 2.55–2.49 (m, 2 H), 2.31 (s, 3 H), 1.01 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 208.2, 168.8, 137.0, 136.9, 132.8, 129.5, 129.2, 128.6 (2×), 127.0, 126.7 (2×), 123.1, 116.2, 49.1, 45.5, 33.4, 33.3, 20.5, 7.6. GC–MS: m/z (%) = 91 (100), 307 (22) [M]⁺. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₂₀H₂₂NO₂: 308.1645; found: 308.1645.