Isshiki Ryota, Kurosawa Miki B, Muto Kei, Yamaguchi Junichiro
Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
Waseda Institute for Advanced Study, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
J Am Chem Soc. 2021 Jul 14;143(27):10333-10340. doi: 10.1021/jacs.1c04215. Epub 2021 Jun 28.
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.
通过芳基硫化物与多种芳基亲电试剂之间的芳基交换反应，开发了一种镍催化的芳基硫化物合成方法。以2-吡啶基硫化物作为硫化物供体，该反应无需使用有气味且有毒的硫醇即可实现芳基硫化物的合成。能够裂解并形成芳基-S键的Ni/dcypt催化剂的使用，对于2-吡啶基硫化物与芳基亲电试剂（包括芳香酯、芳醇衍生物和芳基卤化物）之间的芳基交换反应至关重要。机理研究表明，Ni/dcypt可同时进行芳基硫化物和芳香酯的氧化加成反应，随后生成的芳基-Ni-SR和芳基-Ni-OAr物种之间进行配体交换，以提供芳基交换的化合物。
