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Over the last decades, advances in Ni catalysis have expanded the chemical reactivity of cross-coupling reactions and led to the discovery of catalytic systems that are now widely applied in industrial and academic research. Herein, we report the cross-coupling of aryl tosylates by Ni–NHC catalysis using bulky N-heterocyclic carbene ligands. A notable feature of this operationally-simple method is the combination of ‘fluoride effect’ to minimize homocoupling and bulky NHC ligands, such as IPr* and IPr* MeO , that enhance the activity of Ni in cross-coupling and prevent hydrolysis of sensitive oxygen electrophiles. A broad range of aryl and heteroaryl tosylates underwent cross-coupling with high efficiency. The finding that easily accessible, bulky NHCs with flexible CHPh 2 wingtips enhance the reactivity in Ni–NHC cross-coupling represents a powerful approach for catalysis.more » « less
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Bisz, Elwira; Kardela, Marlena; Piontek, Aleksandra; Szostak, Michal (, Catalysis Science & Technology)The iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling provides a highly economical route to exceedingly valuable alkylated arenes that are widespread in medicinal chemistry and materials science. Herein, we report an operationally-simple protocol for the selective C(sp 2 )–C(sp 3 ) iron-catalyzed cross-coupling of aryl chlorides with Grignard reagents at low catalyst loading. A broad range of electronically-varied aryl and heteroaryl chlorides underwent the cross-coupling using challenging alkyl organometallics possessing β-hydrogens with high efficiency up to 2000 TON. A notable feature of the protocol is the use of environmentally-friendly cyclic urea ligands. A series of guidelines to predict cross-coupling reactivity of aryl electrophiles is provided.more » « less
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Bisz, Elwira; Kardela, Marlena; Szostak, Michal (, ChemCatChem)
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