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. A variety of aryl halides and epoxides featuring diverse functional groups, such as -TMS, -Bpin, -OH, -NH, -CN, and -CHO, were successfully converted into nitriles in moderate-to-good yields. Moreover, the syntheses at gram-scale and application in late-stage cyanation of natural products and drugs reinforces its potentiality.
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http://dx.doi.org/10.3390/molecules29246016 | DOI Listing |
ACS Catal
January 2025
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, United Kingdom.
An aryl radical assay is used to provide information about the formation of aryl radicals from aryl halides in coupling reactions to arenes in the presence of palladium sources and under LED irradiation (λ = 456 nm). The assay uses 2-halo--xylenes as substrates. Aryl radical formation is indicated both by a defined product composition and by signature deuterium isotope effects.
View Article and Find Full Text PDFChemistry
January 2025
Janssen Pharmaceutica NV, chemcial process R&D, BELGIUM.
The manuscript describes the development of an efficient synthetic route to cinnolines, facilitating faster access to JNJ-8003 related Respiratory Syncytial Virus (RSV) non-nucleoside (NNI) inhibitors. Starting from correctly functionalized aryl halides, a Sonogashira reaction followed by SNAr reaction with hydrazine 1,2-dicabroxylate reagents provided dihydrocinnolines directly via in situ 6-endo-dig cyclization. The dihydrocinnolines were conveniently transformed to corresponding cinnolines in one step.
View Article and Find Full Text PDFSci Adv
January 2025
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success in (asymmetric) α-functionalization of carbonyl compounds. However, examples on the use of this activation mode in the transformations of other functional groups are rare, and the combination of SOMO activation with transition metal catalysis is still less explored. In the area of deoxygenative functionalization of amides, intermediates such as iminium ions and enamines were often generated in situ to result in the formation of α-functionalized amines.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, Tamil Nadu-632014, India.
A porphyrin comprising a carboxyl-functionalized pyridine moiety was synthesized and characterized using H NMR, C NMR, FT-IR, powder-XRD, BET, ICP-MS, SEM and EDAX. The proton level (H = 1.19) and energy band gap (1.
View Article and Find Full Text PDFChem Sci
January 2025
University of Regensburg, Institute of Inorganic Chemistry 93040 Regensburg Germany
We present a photocatalytic protocol for the -arylation of carboxylic acids using nickel complexes bearing C8-pyridyl xanthines. Our studies suggest that the underlying mechanism operates independently of external photosensitizers. Stoichiometric experiments and crystallographic studies characterize the catalytically relevant Ni complexes.
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