Ligand-Free Copper-Catalyzed Negishi Coupling of Alkyl-, Aryl-, and Alkynylzinc Reagents with Heteroaryl Iodides†
Surendra Thapa
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorArjun Kafle
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorDr. Santosh K. Gurung
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorAdam Montoya
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorPatrick Riedel
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorCorresponding Author
Prof. Ramesh Giri
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)Search for more papers by this authorSurendra Thapa
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorArjun Kafle
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorDr. Santosh K. Gurung
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorAdam Montoya
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorPatrick Riedel
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Search for more papers by this authorCorresponding Author
Prof. Ramesh Giri
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)
Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA)Search for more papers by this authorWe thank the University of New Mexico (UNM) for financial support, and upgrades to the NMR (NSF grants CHE08-40523 and CHE09-46690) and MS Facilities.
Graphical Abstract
Simply copper: Primary, secondary, and tertiary alkylzinc reagents couple with heteroaryl iodides in the presence of ligand-free CuI without complications arising from β-hydride elimination and rearrangement. The reactions can also be extended to the coupling of aryl- and alkynylzinc reagents. DMF=N,N-dimethylformamide.
Abstract
Reported herein is an unprecedented ligand-free copper-catalyzed cross-coupling of alkyl-, aryl-, and alkynylzinc reagents with heteroaryl iodides. The reaction proceeds at room temperature for the coupling of primary, secondary, and tertiary alkylzinc reagents with heteroaryl iodides without rearrangement. An elevated temperature (100 °C) is required for aryl–heteroaryl and alkynyl–heteroaryl couplings.
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