Herein, we describe nickel-catalyzed nitrile hydroboration with pinacolborane, wherein a tethered NHC-pyridonate ligand enables efficient catalysis (5 mol% [Ni], ≤6 h reaction time) at room temperature. Mechanistic studies, including isolation of the catalytically relevant intermediates, shed light on the cooperative role of the ligand in activating both reagents simultaneously.
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http://dx.doi.org/10.1039/d3cc04229d | DOI Listing |
Molecules
December 2024
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Nitriles are valuable compounds because they have widespread applications in organic chemistry. This report details the nickel-catalyzed reductive cyanation of aryl halides and epoxides with cyanogen bromide for the synthesis of nitriles. This robust protocol underscores the practicality of using a commercially available and cost-effective cyanation reagent.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, 2318 Yuhangtang Road, Hangzhou, 311121, P. R. China.
In industry, the two important nitrile starting materials, adiponitrile and 2-methylglutaronitrile, are primarily manufactured through the well-known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel-catalyzed divergent, one-step double hydrocyanation of 1,3-butadiene to produce either adiponitrile or 2-methylglutaronitrile in high regioselectivity.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada.
Herein, we disclose the nickel-catalyzed reductive cyanation of alkenyl tosylates and triflates. Both cyclic and acyclic alkenyl nitriles are produced in moderate to good yield using 2-(4-methoxyphenyl)-2-methylmalononitrile (MeO-MPMN), a novel transnitrilation, or nitrile transfer, reagent. A robustness screen was undertaken to demonstrate the functional group tolerance of this method.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Leibniz-Institut für Katalyse, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl
January 2025
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Chinese Academy of Sciences), Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, 200032, Shanghai, China.
Organolithium reagents, known for their low cost, ready availability, and high reactivity, allow fast cross-coupling under ambient conditions. However, their direct cross-coupling with fluoroalkyl electrophiles remains a formidable challenge due to the easy formation of thermo-unstable fluoroalkyl lithium species during the reaction, which are prone to decomposition via rapid α/β-fluoride elimination. Here, we exploit heteroatom-stabilized allylic anions to harness the exceptional reactivity of organolithium reagents, enabling the compatibility of difluoroalkyl halides and facilitating versatile and precise fluorine functionality introduction under mild conditions.
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