Synthesis of Aryl Sulfides by Metal‐Free Arylation of Thiols with Diaryliodonium Salts under Basic Conditions**

Abstract

Metal‐free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base enables the C−S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that it proceeds via the inner sphere pathway involving formation of an Ar2I(SR) intermediate, followed by reductive elimination.

Synthesis of Quinoline-2-thiones by Selective Deoxygenative C–H/C–S Functionalization of Quinoline N-Oxides with Thiourea

“…Daryl sulfide 7 was synthesized in a 68% yield from thione 2v and 4-bromoacethophenone under visible-light irradiation using the Miyake’s conditions . The alternative selective S -arylation of thione 2p with a diaryliodonium salt delivered sulfide 8 in an 80% yield . An I 2 -induced reaction of thione 2u with sodium toluene sulfinate gave sulfone 9 under the conditions reported by Quan .…”

“…23 The alternative selective S-arylation of thione 2p with a diaryliodonium salt delivered sulfide 8 in an 80% yield. 24 An I 2 -induced reaction of thione 2u with sodium toluene sulfinate gave sulfone 9 under the conditions reported by Quan. 25 Oxidation of 2b with NCS to afford the corresponding sulfonyl chloride and its immediate reaction with morpholine provided sulfonamide 10 in a 65% overall yield.…”

Metal-free and Atom-efficient Protocol for Diarylation of Selenocyanate by Diaryliodonium Salts

“…16,17 The nucleophilic substitution on chalcogen-center is promising reaction for the design and preparation of the wide range of valuable compounds. [18][19][20][21] Indeed, the exceptional properties of IS as arylation agents led to the development of useful synthetic methods for the chemistry of arylchalcogenides. [22][23][24] However, the diarylation procedures, which include the involvement of both aryl moieties, are still poorly developed.…”

Reaction of Diaryliodonium Salts with Potassium Alkyl Xanthates as an Entry Point to Accessing Organosulfur Compounds

“…Because of the great importance of organosulfur compounds for pharmaceutical chemistry, agrochemistry, and materials science, the development of novel methods for arylation of a variety of S-nucleophiles with iodine­(III) reagents has been attracting a great deal of attention in recent years. As a result, methods for the preparation of aryl sulfides, S -aryl thioimidates, S -aryl dithiocarbamates, sulfoxides, and sulfones have been developed. However, there have not been any reports on the synthesis of aryl thiols employing diaryliodonium salts.…”