Iron-Catalyzed S-Arylation of Benzothiazole with Aryl Iodides under Aqueous Medium: Facile Synthesis of Aryl(2-aminoaryl) Sulfides

Abstract

A simple route for facile access of aryl(2-aminoaryl) sulfide was reported. With the aid of iron(III) chloride catalyst and diamine ligand, benzothiazole was efficiently S-arylated with various aryl iodides (19 examples) in water under air atmosphere. This operationally simple protocol provides aryl(2-aminoaryl) sulfides in moderate to good yields.

Key words

S-arylation - iron - catalysis - benzothiazole - water

• References and Notes

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• 25 General Procedure for the Iron-Catalyzed S-Arylation of Benzothiazole with Aryl Iodides FeCl₃ (32 mg, 20 mol%), trans-1,2-diaminocyclohexane (48 μL, 40 mol%), benzothiazole (108 μL, 1.0 mmol), (hetero)aryl iodide (1.5 mmol), NaOH (0.12 g, 3.0 mmol), and H₂O (1.0 mL) were loaded into a reaction tube equipped with a septum in the presence of Teflon-coated magnetic stirrer bar on bench-top under air. The tube was then placed into a preheated oil bath (110 °C) and stirred for 24 h. After completion of reaction as judged by GC analysis, the reaction tube was allowed to cool to r.t. EtOAc was added for product extraction. The organic layer was separated, and the aqueous layer was further washed with EtOAc (3× ca. 10 mL). The organic part was concentrated under reduced pressure. The crude products were purified by flash column chromatography on silica gel (230–400 mesh) to afford the desired product (see Supporting Information for details). 2-Aminophenyl Phenyl Sulfide (Table 2, Entry 1) Yellow liquid; R_f  = 0.6 (EtOAc–hexane, 1:9). ¹H NMR (400 MHz, CDCl₃): δ = 4.18 (br s, 2 H), 6.81–6.85 (m, 2 H), 7.18 (t, J = 7.6 Hz, 3 H), 7.27–7.32 (m, 3 H), 7.52–7.55 (dd, J = 6.8, 1.2 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 114.39, 115.44, 118.8, 125.5, 126.5, 129.0, 131.2, 136.9, 137.5, 148.9 (see Supporting Information for details). (2-Aminophenyl) 3-Pyridyl Sulfide (Table 3, Entry 1) Brown solid; R_f  = 0.5 (EtOAc–hexane, 1:1). ¹H NMR (400 MHz, CDCl₃): δ = 4.39 (br s, 2 H), 6.71–6.77 (m, 2 H), 7.06–7.09 (q, J = 4.8 Hz, 1 H), 7.20–7.24 (td, J = 8.0, 1.6 Hz, 1 H), 7.27–7.29 (dt, J = 6.4, 1.6 Hz, 1 H), 7.42–7.44 (dd, J = 7.6, 1.2 Hz, 1 H), 8.30–8.32 (dd, J = 4.8, 1.6 Hz, 1 H), 8.38 (d, J = 1.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 112.4, 115.5, 118.8, 123.7, 131.6, 133.8, 134.2, 137.4, 146.4, 147.5, 149.0 (see Supporting Information for details).