A palladium-catalyzed cyanation of aryl halides with hexamethylenetetramine as a safe cyanide source is achieved, providing aromatic nitriles in moderate to good yields. This approach shows good functional group compatibilities and avoids the use of toxic cyanide source.
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http://dx.doi.org/10.1021/acs.joc.7b02373 | DOI Listing |
Chemistry
January 2025
Boehringer Ingelheim RCV GmbH & Co KG: Boehringer Ingelheim RCV GmbH und Co KG, Chemical Development, GERMANY.
A novel screening platform for the nickel-catalyzed cyanation of (hetero)aryl halides relying on the use of air-stable Ni(COD)DQ at low loading is reported. Through high-throughput experimentation (HTE), various ligand and solvent combinations are systematically explored, allowing the fast identification of suitable conditions. This standardized workflow serves as an excellent starting point for selecting other competent nickel precatalysts and for further optimization of reluctant substrates.
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January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
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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.
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January 2025
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences 47 Leninsky Prospect, Moscow, 119991, Russian Federation.
The electrochemically mediated cyanation/annulation process with in situ cyanide ion generation from NHSCN and multi-step oxidative construction of CN-functionalized heterocycles from easily available α-amino esters and pyridine-2-carbaldehydes has been discovered. Depending on the nature of the α-amino ester, 1-cyano-imidazo[1,5-a]pyridine-3-carboxylates, 3-alkyl- and 3-aryl-imidazo[1,5-a]pyridines-1-carbonitriles, and the first reported 4-oxo-4H-pyrido[1,2-a]pyrazine-1-carbonitriles were obtained. The electrosynthesis is carried out in an undivided electrochemical cell under constant current conditions.
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October 2024
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Arylethylamines represent a privileged scaffold in pharmaceutical compounds and form the backbone of many medical drugs, including those used for treating neurological diseases and pain. Their biomedical significance has inspired new synthetic methods that rely on transition metal-catalyzed aminoarylation reaction to an alkene, often in conjunction with a photoredox catalyst or a photosensitizer, and guided by a directing or stabilizing group. Here, we introduce a simple and effective method for azidoarylation of unactivated alkenes under transition metal-free conditions.
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