Highly Regioselective Arylation of 1,2,3-Triazole N-Oxides with Sodium Arenesulfinates via Palladium-Catalyzed Desulfitative Cross-Coupling Reaction

Abstract

A convenient and highly regioselective palladium-catalyzed direct C5-arylation of 1,2,3-triazole N-oxides was developed in the presence of silver carbonate and tripotassium phosphate. This protocol allowed use of sodium arylsulfinates, diphenylphosphine oxide, and triphenylphosphine as arylating reagents to produce 2-aryl-5-aryl-1,2,3-triazole N-oxides in good to excellent yields, providing a complement to the existing methods for the direct arylation of 1,2,3-triazole N-oxides.

Keywords

palladium - 1,2,3-triazole N-oxide - arylation - sodium arylsulfinate

• References and Notes


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• 20 General Procedure for the Preparation of 2-Aryl-5-aryl-1,2,3-triazole N-Oxides To a solution of 2-aryl-1,2,3-triazole N-oxide (0.2 mmol), Pd(OAc)₂ (0.01 mmol), Ag₂CO₃ (0.2 mmol), 1,10-phenanthroline (0.08 mmol), and K₃PO₄ (0.4 mmol) in a mixed solvent of DME–DMF (3:7 v/v, 1 mL) was added sodium arylsulfinate (0.24 mmol) under an air atmosphere, and the mixture was stirred at 80 °C for 12 h. The reaction mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluent: EtOAc–PE, 1:4) to yield the corresponding product 6. All products were characterized by MS, IR, ¹H NMR, and ¹³C NMR spectroscopy.
• 21 Selected Physical and Spectral data for 2-Phenyl-5-p-tolyl-2H-1,2,3-triazole 1-oxide (6aa): white amorphous solid; IR (KBr): 1593, 1135, 510 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.06 (d, J = 8.2 Hz, 2 H, Ar-H), 8.02 (s, 1 H, Ar-H), 7.98 (dd, J = 7.5, 1.4 Hz, 2 H, Ar-H), 7.56 (t, J = 7.5 Hz, 2H, Ar-H), 7.48 (dt, J = 7.5, 1.4 Hz, 1 H, Ar-H), 7.33 (d, J = 8.2 Hz, 2H, Ar-H), 2.43 (s, 3H, CH₃). ¹³C NMR (100 MHz, CDCl3): δ = 139.7, 135.2, 131.1, 129.6, 129.1, 129.0, 127.1, 125.7, 123.3, 122.6, 21.4. MS (ESI): 252 (M + H⁺, 100). Anal. calcd for C₁₅H₁₃N₃O: C, 71.70; H, 5.21; N, 16.72. Found C, 71.35; H, 5.46; N, 16.37.