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Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C−S/C−N Couplings

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 des...

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Detalles Bibliográficos
Autores principales: Martín, M. Trinidad, Marín, Mario, Maya, Celia, Prieto, Auxiliadora, Nicasio, M. Carmen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8456787/
https://www.ncbi.nlm.nih.gov/pubmed/34191385
http://dx.doi.org/10.1002/chem.202101906
Descripción
Sumario: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)(PMe(2)Ar’) (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.