A Metal-Free Cross-Dehydrogenative Coupling Reaction of Amides to Access N-Alkylazoles

Abstract

An iodine-catalyzed cross-dehydrogenative coupling reaction of N-alkyl amides and azoles is reported. The catalytic system provides an efficient method for introducing amides onto azoles, especially onto benzotriazoles.

Key words

cross-dehydrogenative coupling - amides - benzotriazoles - benzimidazoles

• References

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• 16 N-(1H-1,2,3-Benzotriazol-1-ylmethyl)-N-methylacetamide (3a); Typical Procedure A 50 mL Schlenk tube equipped with a stirrer bar was charged with KI (16.6 mg, 0.1 mmol), benzotriazole (59.5 mg, 0.5 mmol), DMA (2 mL), and K₂S₂O₈ (270 mg, 1 mmol) under air. The mixture was then stirred at 80 °C for 6 h (TLC monitoring), poured into H₂O (20 mL), and extracted with EtOAc (3 ×). Then the organic phase was evaporated under vacuum, and the crude product was purified by column chromatography [silica gel, PE–EtOAc (10:1 to 2:1)] to give a colorless oil; yield: 98 mg (96%); ¹H NMR (400 MHz, CDCl₃): d = 8.04 (d, J = 8.3 Hz, 1 H), 7.90 (d, J = 8.7 Hz, 1 H), 7.50 (t, J = 7.5 Hz, 1 H), 7.38 (t, J = 7.6 Hz, 1 H), 6.21 (s, 2 H), 3.11 (s, 3 H), 2.13 (s, 3 H). N-[(6-Chloro-1H-1,2,3-benzotriazol-1-yl)methyl]-N-methylacetamide (3b) and N-[(5-Chloro-1H-1,2,3-benzotriazol-1-yl)methyl]-N-methylacetamide (3b′) Combined yield: 113 mg (95%) 3b Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 7.92–7.85 (m, 2 H), 7.28 (d, J = 8.9 Hz, 1 H), 6.09 (s, 2 H), 3.07 (s, 3 H), 2.08 (s, 3 H); ¹³C NMR (101 MHz, CDCl3): δ = 171.60, 144.66, 134.48, 133.03, 125.65, 120.47, 110.95, 57.72, 35.03, 21.60; HRMS: m/z [M + Na]⁺ calcd for C₁₀H₁₁ClN₄NaO: 261.0514; found: 261.0512. 3b′ Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 8.02 (s, 1 H), 7.88 (dd, J = 8.8, 1.4 Hz, 1 H), 7.48 – 7.43 (m, 1 H), 6.18 (d, J = 1.5 Hz, 2 H), 3.12 (d, J = 1.8 Hz, 3 H), 2.13 (d, J = 1.8 Hz, 3 H); ¹³C NMR (101 MHz, CDCl₃): δ = 128.87, 118.91, 112.23, 57.83, 35.05, 21.63; HRMS: m/z [M + Na]⁺ calcd for C₁₀H₁₁ClN₄NaO: 261.0514; found: 261.0512. N-[(5,6-Dimethyl-1H-1,2,3-benzotriazol-1-yl)methyl]-N-methylacetamide (3c) Colorless oil; yield: 84 mg (72%); ¹H NMR (400 MHz, CDCl₃): δ = 7.76 (s, 1 H), 7.61 (s, 1 H), 6.15 (s, 2 H), 3.08 (d, J = 1.3 Hz, 3 H), 2.40 (d, J = 9.4 Hz, 6 H), 2.13 (d, J = 1.3 Hz, 3 H); ¹³C NMR (101 MHz, CDCl₃): δ = 171.48, 138.40, 134.22, 118.62, 110.22, 57.32, 34.82, 21.75, 20.93, 20.43; HRMS: m/z [M + Na]⁺ calcd for C₁₂H₁₆N₄NaO: 255.1216; found: 255.1219.