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Transition-metal-catalyzed reductive cross-coupling is highly efficient for forming C-C bonds. It earns its limelight from its application by coupling unreactive electrophilic substrates to synthesize a variety of carbon-carbon bonds with various hybridizations (sp, sp, and sp), late-stage functionalization, and bioactive molecules' synthesis. Reductive cross-coupling is challenging to bring selectivity but promising approach. Cobalt is comparatively more affordable than other highly efficient metals e.g., palladium and nickel but cobalt catalysis is still facing efficacy challenges. Researchers are trying to harness the maximum out of cobalt's catalytic properties. Shortly, with efficiency achieved combined with the affordability of cobalt, it will revolutionize industrial applications. This review gives insight into the core of cobalt-catalyzed reductive cross-coupling reactions with a variety of substrates forming a range of differently hybridized coupled products.
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http://dx.doi.org/10.1007/s11030-024-11017-1 | DOI Listing |
J Am Chem Soc
September 2025
Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, California 90095, United States.
Bipyridine-ligated nickel(I) and nickel(0) intermediates are widely proposed in Ni-catalyzed cross-coupling reactions. However, few isolable Ni and Ni complexes with catalytically relevant bipyridine ligands are known, limiting our understanding of these complexes' speciation and reactivity. In this work, we identify and investigate well-defined, isolable (bpy)Ni and (bpy)Ni complexes to characterize their behavior in catalytic systems.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Cross-electrophile coupling (XEC) reactions are considered to be among the most fundamental construction of carbon-carbon bonds in organic chemistry. Traditionally, stoichiometric reductants, including metallic and organic reagents, are required to promote these conversions, resulting in significant waste that contributes to environmental pollution and increased disposal costs. In this study, we report a divided electrochemical synthesis-based cross-coupling platform in which HO is oxidized at the anode surface to generate electrons that produce a lower oxidation state nickel catalyst on the cathode surface, enabling XEC reactions without the need for metallic or organic reagents.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
The enantioselective construction of quaternary carbon stereocenters bearing amine functionalities represents a significant challenge in organic synthesis despite their prevalence in pharmaceutically active compounds. Herein, we report a versatile metallaphotoredox platform for the asymmetric incorporation of amine fragments onto quaternary carbons via coupling of alkene-tethered aryl bromides with readily available α-silylamines. This transformation proceeds under mild conditions without requiring organometallic reagents or stoichiometric reductants.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
College of Polymer Science and Engineering, State Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu, 610065, P.R. China.
Designing long-lived excitons in photocatalysts is crucial for efficient charge separation. However, most of the current organic photocatalysts are characterized by a relatively short exciton lifetime within the range of picoseconds due to localized excitons with large binding energies. Herein, we report the design of ultralong-lived excitons with a lifetime exceeding 8000 ps by constructing metallo-quinoline-incorporated covalent organic frameworks (COFs).
View Article and Find Full Text PDFOrganometallics
June 2025
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48104, United States.
This article describes a detailed investigation of the palladium-catalyzed coupling of aryl (pseudo)halides (ArX) with MSCF to form aryl trifluoromethylthioethers (ArSCF). Mechanistic organometallic studies are used to interrogate two key elementary steps of the catalytic cycle: (1) transmetalation of Pd(Ar)(X) complexes with MSCF and (2) Ar-SCF bond-forming reductive elimination. These studies reveal that tetramethylammonium trifluoromethylthiolate, NMeSCF, exhibits a combination of fast kinetics and high chemoselectivity for transmetalation.
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