Photoredox-Catalyzed Decarboxylative C–H Acylation of Heteroarenes

Abstract

A mild, environmentally friendly, and regioselective acylation of heterocycles with inexpensive carboxylic acids is reported via photoredox catalysis. The strategy is highlighted with good functional group tolerance and substrate scope which could rapidly realize the acylation of various heterocyclic compounds.

Key words

2,2-diethoxyacetic acid - α-keto acids - heterocycles - C–H functionalization - acylation

• References and Notes

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• 18 Procedure A for Compounds 3a–pHeterocycle (0.10 mmol), ammonium persulfate (0.30 mmol) and Cs₂CO₃ (0.20 mmol) were placed in a dry glass tube. Anhydrous DMSO (1 mL) and 2,2-diethoxyacetic acid (0.7 mmol) were injected into the tube by syringe under N₂ atmosphere. The solution was then stirred at room temperature under the irradiation of 15 W blue LEDs strip for 24 h. After completion of the reaction, the mixture was quenched by addition of 1.2 mL of 3.0 M HCl and stirred for another 20 h. Then saturated Na₂CO₃ solution was added to adjust pH to basic. The system was extracted with CH₂Cl₂, the combined organic layers were washed with brine, then dried over anhydrous Na₂SO₄. The desired products were obtained in the corresponding yields after purification by flash chromatography on silica gel eluting with PE and EtOAc.Isoquinoline-1-carbaldehyde (3a)Yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 10.38 (s, 1 H), 9.38–9.22 (m, 1 H), 8.74 (d, J = 5.5 Hz, 1 H), 7.97–7.82 (m, 2 H), 7.83–7.68 (m, 2 H). ¹³C NMR (151 MHz, CDCl₃): δ = 195.79, 195.74, 149.88, 142.54, 136.97, 130.88, 130.15, 127.05, 126.41, 125.80, 125.63. GC-MS (EI): 157.1, 129.1, 102.1, 75.0, 63.1, 51.1, 29.1.Procedure B for Compounds 5a–z,bbHeterocycle (0.10 mmol), ammonium persulfate (0.20 mmol), [Ir{dF(CF₃ppy)}₂(dtbbpy)]PF₆ (0.2 mol%), α-keto acids (1.0 mmol) were placed in a dry glass tube. Anhydrous DMSO (1 mL) was injected into the tube by a syringe under a N₂ atmosphere. The solution was then stirred at room temperature under the irradiation of 15 W blue LEDs strip for 12 h. After completion of the reaction, saturated Na₂CO₃ solution was added to adjust pH to basic. The combined organic layer was washed with brine and then dried over anhydrous Na₂SO₄. The desired products were obtained in the corresponding yields after purification by flash chromatography on silica gel eluting with PE and EtOAc.(4-Methylquinolin-2-yl)(phenyl)methanone (5b)Brownish solid. ¹H NMR (400 MHz, CDCl₃): δ = 8.22 (dd, J = 14.0, 7.9 Hz, 3 H), 8.07 (d, J = 8.3 Hz, 1 H), 7.94 (s, 1 H), 7.77 (t, J = 7.6 Hz, 1 H), 7.72–7.65 (m, 1 H), 7.62 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H), 2.80 (s, 3 H).¹³C NMR (151 MHz, CDCl₃): δ = 194.33, 154.52, 146.72, 145.78, 136.32, 133.18, 131.59, 131.27, 129.86, 129.08, 128.30, 128.27, 123.90, 121.43,19.08. GC-MS (EI): 247.1, 232.1, 218.1, 204.1, 140.0, 105.0, 77.1, 51.1, 28.1.