Selective Diacetoxylation of Disubstituted 1,2,3-Triazoles through Palladium-Catalyzed C–H Activation

Abstract

A simple and efficient selective diacetoxylation of 1,4-disubstituted 1,2,3-triazoles by Pd-catalyzed C–H bond activation is described. PhI(OAc)₂ was used as an acetyloxy source to convert aromatic sp² C–H bonds into C–O bonds with high selectivity by employing a 1,2,3-triazole ring as an elegant directing group. A range of 1,2,3-triazoles bearing two acetyloxy groups can be readily synthesized by the reaction.

Key words

palladium catalysis - regioselectivity - acetoxylation - dia­cetoxytriazoles - C–H activation

• References and Notes

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• 24 Diacetoxyaryltriazines 2a–r; General Procedure A 50 mL pressure tube was charged with the appropriate triazole 1 (0.3 mmol), Pd(OAc)₂ (6.7 mg, 0.03 mmol, 10 mmol%), PhI(OAc)₂ (483 mg, 1.5 mmol, 5.0 equiv), and DCE (2.0 mL) under N₂. The mixture was then stirred at 100 °C for 4 h until triazole 1 was consumed (TLC). The mixture was then mixed with H₂O (15 mL) and extracted with EtOAc (3 × 15 mL). The organic layers were combined, washed with brine (3 × 5 mL), dried (Na₂SO₄), and concentrated under reduced pressure to afford a crude product that was purified by column chromato­graphy (silica gel). 2-[1-(4-Tolyl)-1H-1,2,3-triazol-4-yl]-1,3-phenylene Diacetate (2a) Light-yellow solid; yield: 87 mg (83%); mp 110–111 °C. IR (KBr): 2932, 1766, 1546, 1356, 1230, 1033, 889, 768, 655 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.07 (s, 1 H), 7.63 (d, J = 8.4 Hz, 2 H), 7.44 (t, J = 8.2 Hz, 1 H), 7.35 (d, J = 8.2 Hz, 2 H), 7.14 (d, J = 8.2 Hz, 2 H), 2.44 (s, 3 H), 2.24 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.02, 149.21, 139.50, 139.09, 134.58, 130.35, 129.34, 121.34, 120.92, 120.40, 117.81, 77.32, 77.00, 76.68, 21.08, 21.03. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₈N₃O₄: 352.1292; found: 352.1294. 5-Methyl-2-(1-phenyl-1H-1,2,3-triazol-4-yl)-1,3-phenylene Diacetate (2g) Light-yellow solid; yield: 91 mg (86%); mp 109–110 °C. IR (KBr): 2918, 1766, 1478, 1379, 1196, 1035, 917, 766 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.08 (s, 1 H), 7.75 (dd, J = 8.4, 0.9 Hz, 2 H), 7.55 (dd, J = 10.5, 5.0 Hz, 2 H), 7.46 (dd, J = 8.3, 6.6 Hz, 1 H), 6.95 (s, 2 H), 2.40 (s, 3 H), 2.23 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.11, 148.82, 140.24, 139.78, 136.81, 129.80, 128.81, 121.56, 121.04, 120.39, 114.66, 77.32, 77.00, 76.68, 21.21, 21.00. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₈N₃O₄: 352.1292; found: 352.1295. 5-Methoxy-2-[1-(4-tolyl)-1H-1,2,3-triazol-4-yl]-1,3-phenylene Diacetate (2i) Light-yellow solid: yield: 96 mg (84%,); mp 107–108 °C. IR (KBr): 2921, 1781, 1518, 1378, 1202, 1053, 967, 813 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.00 (s, 1 H), 7.62 (d, J = 8.4 Hz, 2 H), 7.33 (d, J = 8.2 Hz, 2 H), 6.69 (s, 2 H), 3.84 (s, 3 H), 2.43 (s, 3 H), 2.23 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.94, 160.16, 149.85, 139.64, 138.95, 134.58, 130.30, 120.78, 120.31, 110.29, 107.13, 77.32, 77.00, 76.68, 55.69, 21.06, 21.03. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₀H₂₀N₃O₅: 382.1397; found: 382.1400.