Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides

Abstract

Potassium tert-butoxide mediated carbon–chalcogen C–E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 °C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40–45 °C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon–chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.