@article{10272/20060, year = {2021}, url = {http://hdl.handle.net/10272/20060}, abstract = {Ni-catalyzed C−S cross-coupling reactions have received less attention compared with other C-heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C−O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of the type NiCl(allyl)(PMe2Ar’) (Ar’=terphenyl group) efficiently couple a wide range of (hetero)aryl halides, including challenging aryl chlorides, with a variety of aromatic and aliphatic thiols. Aryl and alkenyl tosylates are also well tolerated, demonstrating, for the first time, to be competent electrophilic partners in Ni-catalyzed C−S bond formation. The chemoselective functionalization of the C−I bond in the presence of a C−Cl bond allows for designing site-selective tandem C−S/C−N couplings. The formation of the two C-heteroatom bonds takes place in a single operation and represents a rare example of dual electrophile/nucleophile chemoselective process.}, organization = {We thank FEDER/Ministerio de Ciencia, Innovación y Universi dades-Agencia Estatal de Investigación (Grant CTQ2017-82893-C2-2-R) and US/FEDER/JUNTA, UE (Grant, US126226) for finan cial support}, publisher = {Wiley}, title = {Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C−S/C−N Couplings}, doi = {10.1002/chem.202101906}, author = {Martín, M. Trinidad and Marín, Mario and Maya, Celia and Prieto Cárdenas, María Auxiliadora and Nicasio Jaramillo, María Carmen}, }