Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. The catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.
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http://dx.doi.org/10.1002/cssc.201700329 | DOI Listing |
Comb Chem High Throughput Screen
January 2025
Jiangsu College of Tourism, Yangzhou 225000, P.R. China.
Aims: Organic thiocyanates are important pharmaceutical intermediates. This study aimed to develop a selective and efficient approach for synthesizing organic thiocyanates.
Methods: Under mild reaction conditions, an array of alkenes, KSCN, and diaryliodonium salts are considered good substrates, providing various aryl-substituted alkylthiocyanates with modest to excellent yield.
J Org Chem
January 2025
Laboratory of Pharmaceutical Chemistry, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan.
A one-pot, telescoped transformation of silyl ethers into cyanides that proceeds via silyl-ether oxidation mediated by nitroxyl-radical catalyst and [bis(trifluoroacetoxy)iodo]benzene followed by an imine formation-oxidation sequence using iodine and aqueous ammonia is reported. This transformation is effective for the site-selective transformation of benzylic and allylic silyl ethers in the presence of other silyl ethers. Using an -protected oxime and a catalytic amount of triflic acid instead of iodine/aqueous ammonia is also effective for cyanation.
View Article and Find Full Text PDFChemistry
January 2025
Chemical Development Germany, Boehringer Ingelheim Pharma GmbH & Co. KG, Biberach an der Riß, 88397, 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.
View Article and Find Full Text PDFAcc Chem Res
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.
View Article and Find Full Text PDFMolecules
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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