Synthesis of Perfluoroalkyl-Substituted Oxindoles through Organophotoredox-Catalyzed Perfluoroalkylation of N-arylacrylamides with Perfluoroalkyl Iodides

Abstract

An efficient process was developed for the perfluoroalkylation of N-arylacrylamides through an organocatalyzed photoredox/cyclization reaction of N-arylacrylamides with inexpensive perfluoroalkyl iodide reagents. The reaction employs an inexpensive organic dye, eosin Y, as the photoredox catalyst and is run under irradiation by a 26 W LED lightbulb.

Key words

oxindoles - cyclization - perfluoroalkylation - photoredox reaction

• References and Notes

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• 24a Organocatalyzed Photoredox Perfluoroalkylation/Cyclization of N-Arylacrylamides Perfluoroalkyl Iodides; General ProcedureA 25 mL tube was charged with the appropriate N-arylacrylamide 1 (0.3 mmol), R_FI 2 (0.9 mmol), Cs₂CO₃ (0.3 mmol), and eosin Y (5% mmol). DMA (2 mL) was added and the tube was purged with argon. The mixture was stirred and irradiated with a 26 W compact LED lightbulb at 65 °C for 16 h until the reaction was completed. H₂O (10 mL) and CH₂Cl₂ (10 mL) were added successively to the cooled reaction mixture, the organic phase was separated, and the aqueous phase was further extracted with CH₂Cl₂ (3 × 30 mL). The combined organic layers were dried (Mg₂SO₄) and concentrated under vacuum. The residue was purified performed by flash column chromatography (silica gel).1,3-Dimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dihydro-2H-indol-2-one (3a)Isolated by flash column chromatography [silica gel, PE–EtOAc (50:1)] as a yellow oil; yield: 100 mg (85%). IR (neat): 2979, 1719, 1619, 1470, 1126, 947 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.44 (s, 3 H), 2.54–2.68 (m, 1 H), 2.83–2.95 (m, 1 H), 3.25 (s, 3 H), 6.89 (d, J = 8.0 Hz, 1 H), 7.09 (t, J = 7.6 Hz, 1 H), 7.28 (d, J = 7.6 Hz, 1 H), 7.32 (t, J = 8.0 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 25.8, 26.4, 26.5, 36.9 (t, J = 20.1 Hz), 44.1 (d, J = 1.8 Hz), 108.4, 122.6, 123.1, 123.4, 123.5, 128.5, 128.8, 131.2, 142.8, 178.5.¹⁹F NMR (376 MHz, CDCl₃): δ = –125.64 to –125.42 (m, 2 F), –124.21 (d, J = 9.4 Hz, 2 F), –114.68 to –113.84 (m, 1 F), –108.96 to –108.16 (m, 1 F), –80.76 (t, J = 9.4 Hz, 3 F). HRMS (ESI): m/z [M⁺] calcd for C₁₅H₁₂F₉NO: 393.0775; found: 393.0778.1,3,7-Trimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dihydro-2H-indol-2-one (3b)Isolated by flash column chromatography [silica gel, PE–EtOAc (50:1)] as a yellow oil; yield: 91 mg (75%). IR (neat): 2918, 1722, 1621, 1410, 1145, 670 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.40 (s, 3 H), 2.60 (s, 3 H), 2.50–2.63 (m, 1 H), 2.82–2.95 (m, 1 H), 3.53 (s, 3 H), 6.97 (t, J = 7.6 Hz, 1 H), 7.04 (d, J = 7.2 Hz, 1 H), 7.10 (d, J = 6.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 19.1, 26.4, 29.9, 37.1 (t, J = 20.3 Hz), 44.5 (d, J = 1.9 Hz), 120.1, 121.3, 121.4 (2 C), 122.5, 131.9, 132.2 (2 C), 140.6, 179.3. ¹⁹F NMR (376 MHz, CDCl₃): δ = –125.71 to –125.50 (m, 2 F), –124.27 (d, J = 9.8 Hz, 2 F), –114.03 to –113.94 (m, 1 F), –109.01 to –108.24 (m, 1 F), –80.86 to –80.79 (m, 3 F). HRMS (ESI): m/z [M⁺] calcd for C₁₆H₁₄F₉NO: 407.0932; found: 407.0931.