Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction
Ryota Isshiki, Miki B. Kurosawa, Kei Muto and Junichiro Yamaguchi*
*Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan, Email: junyamaguchiwaseda.jp
R. Isshiki, M. B. Kurosawa, K. Muto, J. Yamaguchi, J. Am. Chem. Soc., 2021, 143, 10333-10340.
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The use of 2-pyridyl sulfides as sulfide donors enables a synthesis of aryl sulfides without using odorous and toxic thiols in the presence of a Ni/dcypt catalyst capable of cleaving and forming aryl-S bonds. This aryl exchange reaction works between 2-pyridyl sulfides and a broad range of aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides.
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A 20-mL glass vessel equipped with J. Young® O-ring tap containing a magnetic stirring bar was dried with a heat-gun in vacuo and filled with N2 gas after cooling to room temperature. To this were added an aryl electrophile (0.80 mmol, 2.0 equiv), Zn (26.2 mg, 0.40 mmol, 1.0 equiv), and dcypt (28.6 mg, 0.060 mmol, 15 mol %). The vessel was introduced inside a N2 atmosphere glovebox. In a glovebox, to the vessel was added Ni(cod)2 (11.0 mg, 0.040 mmol, 10 mol %), which was then capped with a rubber septum and taken out of the glovebox. To this vessel were added 2-pyridyl sulfide (0.40 mmol, 1.0 equiv) and then added toluene (1.6 mL). The vessel was sealed with O-ring tap and then heated at 150 °C for 24 hours in an oil bath or a 9-well reaction block with stirring. After cooling the reaction mixture to room temperature, the mixture was passed through a short silica-gel pad with EtOAc as an eluent. The filtrate was concentrated in vacuo. The residue was purified by Isolera® or PTLC to afford the corresponding aryl sulfide.