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Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C−S/C−N Couplings
Author(s) -
Martín M. Trinidad,
Marín Mario,
Maya Celia,
Prieto Auxiliadora,
Nicasio M. Carmen
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101906
Subject(s) - electrophile , aryl , chemistry , nucleophile , tandem , heteroatom , chemoselectivity , electrophilic aromatic substitution , combinatorial chemistry , catalysis , medicinal chemistry , organic chemistry , alkyl , materials science , composite material
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.