An additive-free nickel-catalyzed α-allylation of aldehydes with allyl alcohol is reported. The reaction is promoted by 1 mol % of in situ formed nickel complex in methanol, and water is the sole by-product of the reaction. The experimental conditions allow the conversion of various α-branched aldehydes and α,β-unsaturated aldehydes as nucleophiles. The same catalyst and reaction conditions enabled a tandem aldol condensation of aldehyde/α-allylation reaction.
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http://dx.doi.org/10.1002/anie.201703486 | DOI Listing |
Org Lett
January 2025
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian, Liaoning, People's Republic of China.
A straightforward and efficient nickel-catalyzed cyclization/carbonylation transformation of -allylbromoacetamides toward the synthesis of 2-pyrrolidinone derivatives has been developed with arylboronic acids as the reaction partner. This transformation proceeds through a sequential single-electron-transfer pathway via 5-- cyclization and carbonyl insertion steps, furnishing a variety of 2-pyrrolidinone derivatives in good yields. Various useful functional groups were well tolerated.
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January 2025
Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, Guangdong 511436, China.
Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination and cyclization of terminal alkynes with organoboronic acids and anthranils for facile and modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent and a redox buffer to suppress the generation of an off-cycle Ni(0) complex. Moreover, the anionic acetylacetonate (acac) ligand was found to be vital to ensure a productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.
View Article and Find Full Text PDFACS Catal
January 2025
Fakultät für Chemie und Pharmazie, Universität Regensburg, Regensburg 93040, Germany.
Transition metal catalysis is crucial for the synthesis of complex molecules, with ligands and bases playing a pivotal role in optimizing cross-coupling reactions. Despite advancements in ligand design and base selection, achieving effective synergy between these components remains challenging. We present here a general approach to nickel-catalyzed photoredox reactions employing -butylamine as a cost-effective bifunctional additive, acting as the base and ligand.
View Article and Find Full Text PDFBeilstein J Org Chem
January 2025
Sagami Chemical Research Institute, 2743-1 Hayakawa, Ayase, Kanagawa 252-1193, Japan.
2-Fluorobenzofurans underwent efficient nickel-catalyzed coupling with arylboronic acids through the activation of aromatic C-F bonds. This method allowed us to successfully synthesize a range of 2-arylbenzofurans with various substituents. The reaction, which proceeded under mild conditions, involved β-fluorine elimination from nickelacyclopropanes formed by the interaction of 2-fluorobenzofurans with zero-valent nickel species.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China.
Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, -selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range of cyclic or acyclic quaternary carbon centers under mild conditions. The utilization of the diimine ligand is critical for high reactivity and chemoselectivity.
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