Copper-Catalyzed Base-Free N-Arylation of 8-Aminoquinoline Amides through Chelation Assistance

Abstract

A new and efficient approach for the N-arylation of 8-aminoquinoline amides with diaryliodonium salts has been developed. This chelation-assisted selective C–N cross-coupling reaction gave the desired N-arylated 8-aminoquinoline in moderate to good yields. In contrast to previous reports, no additional ligands and bases are used in this transformation. In addition, the anion of the diaryliodonium salt plays an important role in the success of the process.

Key words

copper catalysis - diaryliodonium salts - arylation - aminoquinolines - chelation assistance - quinolinylarylamides

• References and Notes


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• 12 N-Aryl-N-quinolin-8-ylaroylamides 3aa–3ma; General Procedure An oven-dried Schlenk tube (10 mL) equipped with a magnetic stirrer bar was charged with the appropriate N-quinolin-8-ylaroylamide 1 (0.3 mmol), diaryliodonium hexafluorophosphate 2 (0.6 mmol), Cu(OAc)₂ ^. H₂O (20 mol%, 0.06 mmol), and 4 Å MS (40 mg). DCE (3.0 mL) was then added from a syringe, and the mixture was stirred for 48 h at 80 °C in air. H₂O (6 mL) was added to quench the reaction, and the resulting mixture was extracted with EtOAc (×2). The combined organic extracts were washed with brine, dried (Na₂SO₄), and concentrated. The crude product was purified by flash column chromatography [silica gel, PE–EtOAc (3:1)]. N-Phenyl-N-quinolin-8-ylbenzamide (3aa) Colorless solid; yield: 71 mg (73%); mp 125–128 °C. IR (KBr): 3054, 1660, 1594, 1493, 1463, 1343, 1310, 1269, 1177, 1132, 1075, 1028, 825, 789, 700 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.89–8.91 (m, 1 H), 8.07–8.09 (m, 1 H), 7.70–7.72 (m, 1 H), 7.57–7.62 (m, 3 H), 7.45–7.49 (m, 1 H), 7.32–7.35 (m, 1 H), 7.22–7.24 (m, 4 H), 7.09–7.16 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.6, 150.7, 144.7, 144.4, 141.8, 136.8, 135.8, 129.7, 129.3, 129.2, 128.9, 128.7, 127.6, 127.4, 126.9, 126.3, 125.8, 121.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₂H₁₇N₂O: 325.13354; found: 325.13327.