Synthesis of N-Arylsulfonamides by a Copper-Catalyzed Reaction of Chloramine-T and Arylboronic Acids at Room Temperature

Abstract

A copper-catalyzed Chan–Lam-coupling-like reaction of a (het)arylboronic acid and chloramine-T (or a related compound) has been developed for the synthesis of N-arylsulfonamides at room temperature in moderate to good yields, with good tolerance of functional groups. In this process, it is believed that chloramine-T serves as an electrophile.

Key words

chloramine-T - cross-coupling - copper catalysis - arylboronic acids - arylsulfonamides

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• 16 Reaction of Chloramines 2 with Arylboronic Acids 1; General Procedure A test tube equipped with a stirrer bar was charged with the appropriate chloramine 2 (0.3 mmol), arylboronic acid 1 (0.36 mmol), and t-BuOK (50.5 mg, 0.45 mmol). A solution of Cu(OAc)₂ (2.7 mg, 0.015 mmol) in EtOH (1.5 mL) was then added, and the mixture was stirred under air at RT for 12 h. The heterogeneous mixture was then diluted with EtOAc (1 mL), and the resulting mixture was filtered through a pad of silica gel, which was washed with EtOAc (3 mL). The organic solutions were combined, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel, PE–EtOAc). 4-Methyl-N-phenylbenzenesulfonamide (3a) White solid; yield: 46 mg (62%); mp 100–101 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.67 (d, J = 8.3 Hz, 2 H), 7.22 (t, J = 7.9 Hz, 4 H), 7.09 (dd, J = 9.4, 8.3 Hz, 3 H), 6.97 (s, 1 H), 2.37 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.87, 136.58, 136.14, 129.65, 129.30, 127.29, 125.30, 121.57, 21.52.