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.

One-Pot Synthesis of Diaryl Sulfonamides using an Iron- and Copper-Catalyzed Aryl C–H Amidation Process

“…)phenyl]carbamate (7j) 34 The reaction was performed according to the general procedure using benzyl (4-aminophenyl)carbamate (0.114 g, 0.500 mmol) and p-toluenesulfonamide (0.128 g, 0.750 mmol). The iodination step was carried out at 40 °C for 4 h and the N-arylation step at 110 °C for 40 h. Purification by flash column chromatography (10% ethyl acetate in chloroform) gave the title compound.…”

“…Yield: 0.130 g (65%); white solid; mp 161-163 °C (Lit. 34 162-163 °C). 35 The reaction was performed according to the general procedure using iron(III) chloride (0.00406 g, 0.0250 mmol), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (0.0220 mL, 0.0750 mmol), N-tosylaniline (0.124 g, 0.500 mmol) and p-toluenesulfonamide (0.128 g, 0.750 mmol).…”

“…1 H NMR (500 MHz, CDCl 3 ):  = 3.77 (s, 3 H, OCH 3 ), 6.47 (br s, 1 H, NH), 6.74-6.81 (m, 2 H, 3-H and 5-H), 6.94-7.01 (m, 2 H, 2-H and 6-H), 7.37-7.42 (m, 2 H, 3′-H and 5′-H), 7.59-7.64 (m, 2 H, 2′-H and 6′-H). 13 MS (EI): m/z = 297 (M + ) (73), 122 (100), 111 (23), 95 (34), 83 (27), 75 (17), 65 (7), 52 (13).…”

Facile Chan‐Lam coupling using ferrocene tethered N‐heterocyclic carbene‐copper complex anchored on graphene

“…Due to broad therapeutic potential, synthesis of N ‐aryl sulfonamides represents significant area of research in organic synthesis. Some of the most prominent methods for their synthesis include copper catalyzed reaction of sulfonyl azides or sulfonamides with boronic acids, Pd(OAc) 2 mediated N ‐arylation of sulfonamides using aryl halides or aryl triflates, copper promoted reaction of chloramine‐T and arylboronic acids, Pd assisted cross‐coupling of methanesulfonamide with aryl halides,[19a] transition metal free reaction of o ‐silylaryl triflates with sulfonamides,[19b] Pd promoted aminosulfonylation of aryl iodides[19c] and iron mediated coupling of nitroarenes and sodium sulfonate [19d]. Amongst these, copper catalyzed reaction of sulfonyl azides and boronic acids represents most elegant protocol due to wide substrate scope, mild reaction conditions and potential synthetic utility.…”