Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

Abstract

A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl–S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl–Ni–SR and aryl–Ni–OAr species to furnish aryl exchanged compounds.

Recent Trends in Nickel‐Catalyzed C−S Bond Formation

“…These types of transformations are synthetically valuable because they circumvent the use of nucleophilic parts, which offers low functional group tolerance and deactivation of the catalyst. In 2021, Yamaguchi and co‐workers developed aryl sulfide synthesis using Ni/dcypt/Zn catalyst by an aryl exchange reaction between 2‐pyridyl sulfide as a sulfide donor and various sulfide acceptors (aryl electrophiles) like aromatic esters, arenols and haloarens [86] . Usually, in conventional methods, C−S bonds are formed by the metal‐catalyzed reaction between aryl electrophiles with highly poisonous and odorous thiols.…”

“…In 2021, Yamaguchi and co-workers developed aryl sulfide synthesis using Ni/dcypt/Zn catalyst by an aryl exchange reaction between 2-pyridyl sulfide as a sulfide donor and various sulfide acceptors (aryl electrophiles) like aromatic esters, arenols and haloarens. [86] Usually, in conventional methods, CÀ S bonds are formed by the metal-catalyzed reaction between aryl electrophiles with highly poisonous and odorous thiols. This developed aryl exchange reaction avoid the use of thiols, and the Ni-catalyst are (10 mol%) and 1,2-bis(dicyclohexylphosphino)ethane (dcypt) (15 mol%) along with 1 equivalent of zinc in toluene at 150 °C for 24 hours (Scheme 36).…”

Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters

“…In this context, methods for transition-metal-catalyzed functional group exchange have been reported using Pd catalysis between aroyl chlorides and iodoarenes by Ar–C­(O)­Cl/Ar′–I exchange. , Subsequently, the Ni-catalyzed aryl exchange between haloarenes/arenols and 3-pyridyl esters was reported by Ar–X/3-py–CO 2 Ar′ exchange . Most recently, Yamaguchi and coworkers reported Ni-catalyzed aryl sulfide synthesis by aryl exchange between 2-pyridyl sulfides and aromatic esters by 2-py–SR/Ar–CO 2 Ar′ exchange (Figure B) …”

“…In light of the report by Yamaguchi and our own work, ,− we considered it appropriate to disclose our findings on the synthesis of aryl sulfides by Pd-catalyzed double-decarbonylative aryl exchange between amides and thioesters (Figure C). In contrast with the Ni-catalyzed method, there are three distinct features of our approach: (1) The reaction uses amides as Ar–C­(O)­X electrophiles (cf. esters), which enables translation of the aryl exchange manifold to amide bonds.…”

“…Furthermore, the scope of the thioester component accommodates electron-neutral ( 2a , 2k ), electron-rich ( 2l ), electron-deficient ( 2m ), sterically hindered ( 2n ), heterocyclic ( 2o ), and aliphatic ( 2p ) substrates (Figure B). This is another difference with the Ni protocol, which is limited to aliphatic 2-pyridyl sulfides …”