Lanthanum Pentafluorobenzoate-Catalyzed Aerobic Oxidative Olefination of Benzylamines with 2-Methylquinoline through Deamination and C–H Bond Functionalization

Abstract

An efficient direct aerobic oxidative olefination of the methyl groups of 2-methylquinolines with benzylamines in the presence of a rare-earth-metal Lewis acid catalyst to give 2-styrylquinolines was successfully developed. Preliminary mechanistic studies revealed that the oxidative olefination reaction proceeds through a Lewis acid-catalyzed 2-methylquinoline–aldehyde condensation and an amine–aldehyde condensation.

Key words

quinolines - C–H functionalization - olefination - oxidation - Lewis acid

• References and Notes

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• 17 (E)-2-Styrylquinolines 3a–x; General Procedure La(Pfb)₃ (0.015 mmol) was added to a solution of the appropriate 2-methylquinoline 1 (0.3 mmol) and amine 2 (0.6 mmol) in toluene (0.5 mL), and the mixture was stirred at 120 °C for 24 h. The mixture was then concentrated under vacuum, and the product was isolated by column chromatography (silica gel, hexane–EtOAc). 2-[(E)-2-Phenylvinyl]quinoline (3a) White solid: yield: 71.9 mg (90%); mp 98–100 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.13 (d, J = 8.8 Hz, 1 H), 8.08 (d, J = 8.4 Hz, 1 H), 7.79 (d, J = 8.0 Hz, 1 H), 7.73–7.64 (m, 5 H), 7.50 (td, J = 8.0 Hz, 1.2 Hz, 1 H), 7.44–7.39 (m, 3 H), 7.35–7.31 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 156.0, 148.3, 136.5, 136.4, 134.5, 129.8, 129.2, 129.0, 128.8, 128.7, 127.5, 127.4, 127.3, 126.2, 119.3. HRMS (ESI): [M + H]⁺ calcd for C₁₇H₁₄N: 232.1126; found: 232.1128.