Gold(I)-Catalyzed Iodination of Arenes

Abstract

A wide variety of electron-rich arenes were efficiently converted into the corresponding iodinated compounds via a gold(I)-catalyzed reaction under mild conditions.

Key words

gold - homogeneous catalysis - iodination - arenes - electrophilic aromatic substitution

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• 18 General Procedure: To a stirred solution of the substrate (1 mmol) in CH₂Cl₂ or (CH₂Cl)₂ (0.1 M) were added Ph₃PAuNTf₂ (0.025 mmol, 19 mg; complex Ph₃PAuNTf₂–toluene, 2:1) followed by N-iodosuccinimide (1.1 mmol, 248 mg). The resulting solution was stirred at r.t. or under reflux until complete conversion of the starting material. After removal of the solvent under reduced pressure, the crude material was purified by flash column chromatography using different gradients of hexanes and EtOAc to obtain the pure desired products. 5-Iodo-2-methoxynitrobenzene (17): compound 17 was prepared in 97% yield according to the general procedure; yellow solid; mp 96–98 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.09 (d, J = 2.0 Hz, 1 H), 7.79 (dd, J = 8.8, 2.0 Hz, 1 H), 6.86 (d, J = 8.8 Hz, 1 H), 3.93 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 152.8, 142.7, 140.3, 133.9, 115.6, 80.6, 56.6. IR (neat): 3109, 3078, 2943, 2851, 1597, 1562, 1512, 1481, 1442, 1343, 1269, 1254, 1188, 1165, 1095, 1015 cm^–1. HRMS (EI+): m/z calcd for C₇H₆O₃IN: 278.9392; found: 278.9383.