Selective Copper-Catalyzed N-Arylation of Lactams with Arylboronic Acids under Base- and Ligand-Free Conditions

Abstract

An oxidative copper-catalyzed cross-coupling of arylboronic acids with various ring-size lactams has been developed. The N-arylated lactams were obtained in moderate to excellent yields without any additional bases, ligands, or additives. This reaction shows complete selectivity for N-arylation of lactams in the presence of a hydroxyl group.

Key words

amides - catalysis - copper - cross-coupling - oxidation

• References and Notes

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• 24 Typical Procedure: Aryl boronic acid (1.0 mmol), CuI (5 mol%), amide (3.0 mmol), and DMSO (1.0 mL) were added to a reaction vial, and the mixture was stirred at room temperature for 10 min. A 70% aqueous solution of TBHP (1.1 mmol) was added to the reaction mixture dropwise over 5 min. The reaction vial was then immersed in a preheated oil bath and the progress of reaction was followed by TLC. Upon completion of reaction, the cooled mixture was partitioned between water and ethyl acetate. The aqueous layer was further extracted with ethyl acetate, and the combined organic layers were washed with brine, dried over Na₂SO₄, filtered, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (hexane–ethyl acetate) to give the desired N-aryl lactam.
• 25 1-(4-Hydroxyphenyl)pyrrolidin-2-one (3a): Yield: 149 mg (84%); dark-red solid; mp 165–167 °C (Lit.¹ 167 °C). IR (KBr): 3134, 2926, 1686, 1650, 1517, 1413, 1308, 1274, 1235, 1203, 1220, 833, 657, 507, 460 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.33 (d, 2 H, J = 9.0 Hz), 6.78 (d, 2 H, J = 8.8 Hz), 3.82 (t, J = 6.9, 7.1 Hz, 2 H), 2.61 (t, J = 7.9, 8.3 Hz, 2 H), 2.11–2.21 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 174.5, 153.4, 131.7, 122.7, 115.7, 49.7, 32.3, 18.0. MS (ESI): m/z = 178 [M + H]⁺. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₁₂O₂N: 178.0862; found: 178.0863.