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1. Cobalt−NHC Catalyzed C(sp 2 )−C(sp 3 ) and C(sp 2 )−C(sp 2 ) Kumada Cross‐Coupling of Aryl Tosylates with Alkyl and Aryl Grignard Reagents

   https://doi.org/10.1002/cctc.202001347  

   Piontek, Aleksandra ; Ochędzan‐Siodłak, Wioletta ; Bisz, Elwira ; Szostak, Michal ( November 2020 , ChemCatChem)

   The first cobalt‐catalyzed cross‐coupling of aryl tosylates with alkyl and aryl Grignard reagents is reported. The catalytic system uses CoF₃and NHCs (NHC=N‐heterocyclic carbene) as ancillary ligands. The reaction proceeds via highly selective C−O bond functionalization, leading to the corresponding products in up to 98 % yield. The employment of alkyl Grignard reagents allows to achieve a rare C(sp²)−C(sp³) cross‐coupling of C−O electrophiles, circumventing isomerization and β‐hydride elimination problems. The use of aryl Grignards leads to the formation of biaryls. The C−O cross‐coupling sets the stage for a sequential cross‐coupling by exploiting the orthogonal selectivity of the catalytic system.

    

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2. Iron-Catalyzed C(sp 2 )–C(sp 3 ) Cross-Coupling of Chlorobenzenesulfonamides with Alkyl Grignard Reagents: Entry to Alkylated Aromatics

   https://doi.org/10.1021/acs.joc.8b02886  

   Bisz, Elwira ; Szostak, Michal ( December 2018 , The Journal of Organic Chemistry)
3. N -Butylpyrrolidone (NBP) as a non-toxic substitute for NMP in iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling of aryl chlorides

   https://doi.org/10.1039/D1GC02377B  

   Bisz, Elwira ; Koston, Martina ; Szostak, Michal ( October 2021 , Green Chemistry)

   Although iron catalyzed cross-coupling reactions show extraordinary promise in reducing the environmental impact of more toxic and scarce transition metals, one of the main challenges is the use of reprotoxic NMP (NMP = N -methylpyrrolidone) as the key ligand to iron in the most successful protocols in this reactivity platform. Herein, we report that non-toxic and sustainable N -butylpyrrolidone (NBP) serves as a highly effective substitute for NMP in iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling of aryl chlorides with alkyl Grignard reagents. This challenging alkylation proceeds with organometallics bearing β-hydrogens with efficiency superseding or matching that of NMP with ample scope and broad functional group tolerance. Appealing applications are demonstrated in the cross-coupling in the presence of sensitive functional groups and the synthesis of several pharmaceutical intermediates, including a dual NK1/serotonin inhibitor, a fibrinolysis inhibitor and an antifungal agent. Considering that the iron/NMP system has emerged as one of the most powerful iron cross-coupling technologies available in both academic and industrial research, we anticipate that this method will be of broad interest. 

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4. Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp 3 )–C(sp 3 ) Cross Coupling

   https://doi.org/10.1021/jacs.3c03337  

   Gao, Yang ; Zhang, Benxiang ; He, Jiayan ; Baran, Phil S. ( May 2023 , Journal of the American Chemical Society)
5. Iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling at low catalyst loading

   https://doi.org/10.1039/C8CY02374C  

   Bisz, Elwira ; Kardela, Marlena ; Piontek, Aleksandra ; Szostak, Michal ( March 2019 , 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. 

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