Iron-Catalyzed Tandem Radical Addition/Cyclization: Highly Efficient Access to Methylated Quinoline-2,4-diones

^◊ These authors contributed equally to this work.

Abstract

A visible-light-induced and iron-catalyzed oxidative radical addition/cyclization cascade reaction of N-(o-cyanoaryl)acrylamides with dimethyl sulfoxide has been developed. The method exhibits a wide substrate scope and an excellent functional-group tolerance, thus providing an efficient and convenient access to a variety of methylated quinoline-2,4-diones.

Key words

photochemical reaction - iron catalysis - methylation - quinolinediones - cascade reaction

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• 20 3-Ethyl-1,3-dimethylquinoline-2,4(1H,3H)-diones 2a–p; General Procedure FeSO₄·7H₂O (0.015 mol, 15 mol%) and the appropriate N-(2-cyanoaryl)-N-methylmethacrylamide 1 (0.1 mol, 1.0 equiv) were sequentially weighed into a tube, and DMSO (1.0 mL) and 30% aq H₂O₂ (300 μL) were added from a syringe. The mixture was then irradiated by a 6 W blue LED at r.t. under air for 12 h. The volatile solvent and reagents were removed by rotary evaporation, and the residue was purified by flash chromatography (silica gel, PE–EtOAc). 3-Ethyl-1,3-dimethylquinoline-2,4(1H,3H)-dione (2a) Colorless oil; yield: 15.4 mg (71%). ¹H NMR (600 MHz, CDCl₃): δ = 8.02 (dd, J = 7.7, 1.6 Hz, 1 H), 7.63 (ddd, J = 8.4, 7.3, 1.7 Hz, 1 H), 7.23–7.11 (m, 2 H), 3.49 (s, 3 H), 2.10–1.87 (m, 2 H), 1.46 (s, 3 H), 0.79 (t, J = 7.4 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 197.59, 173.78, 143.22, 135.90, 127.95, 122.97, 120.43, 114.68, 57.87, 32.71, 29.70, 21.97, 9.47. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₆NO₂: 218.1181; found: 218.11755. N-(2-Cyanophenyl)-2-hydroxy-2-methylbutanamide (3a) Colorless oil; yield: 15.9 mg (73%). ¹H NMR (600 MHz, CDCl₃): δ = 9.41 (s, 1 H), 8.56–8.41 (m, 1 H), 7.60 (td, J = 7.6, 7.1, 1.5 Hz, 3 H), 7.18 (td, J = 7.7, 0.9 Hz, 1 H), 2.02 (dq, J = 14.9, 7.5 Hz, 1 H), 1.73 (dq, J = 14.8, 7.5 Hz, 1 H), 1.54 (s, 3 H), 0.98 (t, J = 7.5 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 174.31, 140.17, 134.16, 132.26, 124.12, 120.62, 116.23, 102.28, 33.34, 26.34, 7.82. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₅N₂O₂: 219.1134; found: 219.11276.