Palladium-Catalyzed Direct and Regioselective C-5 Desulfitative Arylation of Thiazolo[3,2-b]-1,2,4-triazoles with Sodium Sulfinates

Abstract

An efficient Pd(OAc)₂-catalyzed direct arylation of thi­azolo[3,2-b]-1,2,4-triazoles with sodium sulfinates has been developed. The reaction shows high regioselectivity, good reaction efficiency and excellent functional group compatibility. This approach provides a useful protocol for the preparation of functionalized thiazolo[3,2-b]-1,2,4-triazole derivatives.

Key words

desulfitative arylation - C–H activation - thiazolo[3,2-b]-1,2,4-triazoles - sodium arylsulfinates

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• 22 General Procedure for the Synthesis of 3 and 4: A reaction vessel was charged with thiazolo[3,2-b]-1,2,4-triazoles 1 (0.5 mmol), sodium arylsulfinates 2 (1 mmol), Pd(OAc)₂ (5 mol%), Cu(OAc)₂ (2 equiv), and dioxane–diglyme (1:2; 1 mL). The mixture was stirred at 120 °C and monitored by TLC. After the completion of the reaction, the mixture was poured into H₂O (10 mL), and extracted with EtOAc (3 × 10 mL). The combined extract was dried with anhyd MgSO₄. The solvent was removed and the crude product was separated by column chromatography (eluted with petroleum ether–EtOAc) to give the desired products 3 and 4. 6-Methyl-5-o-tolylthiazolo[3,2-b]-1,2,4-triazole(3b): The product was isolated as a colorless oil in 73% yield (84 mg). ¹H NMR (400 MHz, CDCl₃): δ = 8.16 (s, 1 H), 7.28–7.36 (m, 4 H), 2.37 (s, 3 H), 2.29 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.2, 138.2, 131.5, 130.6, 129.8, 129.4, 126.1, 126.0, 123.9, 20.0, 11.2. ESI–MS: m/z (%) = 230 (100) [M + H]⁺. Anal. Calcd for C₁₂H₁₁N₃S: C, 62.86; H, 4.84; N, 18.33. Found: C, 62.81; H, 4.80; N, 18.28. 2,6-Dimethyl-5-phenylthiazolo[3,2-b]-1,2,4-triazole (4a): The product was isolated as a white solid in 78% yield (90 mg); mp 72–73 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.48 (m, 5 H), 2.60 (s, 3 H), 2.57 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 165.3, 155.3, 131.3, 129.1, 129.0, 128.8, 124.9, 124.0, 14.9, 11.7. ESI–MS: m/z (%) = 230 (100) [M + H]⁺. Anal. Calcd for C₁₂H₁₁N₃S: C, 62.86; H, 4.84; N, 18.33. Found: C, 62.82; H, 4.81; N, 18.27.