One-Pot Synthesis of Amine-Substituted Aryl Sulfides and Benzo[b]thiophene Derivatives

Abstract

A series of amine-substituted aryl sulfides have been synthesized from nitroaryl halides via a simple one-pot procedure involving metal-free C-S cross-coupling and in situ nitro group reduction. Various nitroaryl halides were reacted with thiols in recyclable poly(ethylene glycol) to afford the amine-substituted aryl sulfides in high yield. Additionally, the cross-coupling reactions of nitro- and aldehyde-substituted aryl halides with benzyl thiols under the same reaction conditions were demonstrated to afford benzothiazole and phenylbenzo[b]thiophene derivatives.

Copper Powder Catalyzed Direct Ring‐Opening Arylation of Benzazoles with Aryl Iodides in Polyethylene Glycol

“…The reactions with aryl iodides bearing either electron-rich or electron-deficient substituents at the phenyl moiety proceeded efficiently to afford the desired products (i.e., 3aa-3da) in excellent yields in short times. [6] Interestingly, in our case, the nitro group did not disturb the high selectivity and remained intact in PEG-600. This protocol could tolerate halides such as F and Br, which can be used for further functionalization.…”

Dimethyl Sulfoxide/Potassium Hydroxide: A Superbase for the Transition Metal‐Free Preparation of Cross‐Coupling Products

“…As a starting point, arylations of thiols using KOH in DMSO were studied (Table 1). 15 To our delight, reactions between thiophenol and electron‐poor aryl halides were greatly facilitated leading to the corresponding cross‐coupling products in good to high yields (entries 1 and 2) 16,17. The reactions had to be performed at 130 °C, because at lower temperature (110 °C) the conversions remained incomplete.…”

Metal-Free Iodine-Catalyzed Direct Arylthiation of Substituted Anilines with Thiols

“…The tube was evacuated twice and backfilled with nitrogen, and DTBP (2.5 mmol) was added into the tube. The tube was sealed and then the mixture was allowed to stir under nitrogen atmosphere at 120 o C for 24 h. 25 Compound 3n was obtained in 13% yield (12 mg) according to the general procedure. Eluent petroleum ether/ethyl acetate (20:1 7, 134.1, 122.0, 112.4, 36.5, 31.6, 30.7, 21.9, 13.7; HRMS m/z calcd.…”