The rapid transformation of pharmaceuticals and agrochemicals enables access to unexplored chemical space and thus has accelerated the discovery of novel bioactive molecules. Because arylacetic acids are regarded as key structures in bioactive compounds, new transformations of these structures could contribute to drug/agrochemical discovery and chemical biology. This work reports carbon-nitrogen and carbon-oxygen bond formation through the photoredox-catalyzed decarboxylation of arylacetic acids. The reaction shows good functional group compatibility without pre-activation of the nitrogen- or oxygen-based coupling partners. Under similar reaction conditions, carbon-chlorine bond formation was also feasible. This efficient derivatization of arylacetic acids makes it possible to synthesize pharmaceutical analogues and bioconjugates of pharmaceuticals and natural products.
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http://dx.doi.org/10.1002/chem.201802143 | DOI Listing |
Molecules
December 2024
National Institute for Research and Development of Isotopic and Molecular Technologies, Str. Donat 67-103, 400293 Cluj-Napoca, Romania.
The recently developed phenoplast-related polymer, poly(benzofuran--arylacetic acid), presents a versatile molecular structure containing lactone and carboxylic acid functionalities that offer significant flexibility in creating cured materials with tailored properties for diverse applications, wherein also the thermal conductivity is an important factor. This study analyses the possibility of forming amide moieties of poly(benzofuran--arylacetic acid) with diamines resulting in cross-linked products in order to control its thermal properties. The cross-linking process is achieved by utilizing three distinct diamines, 1,6-diaminohexane, -xylylenediamine, and 4,7,10-trioxa-1,13-tridecanediamine, each possessing different degrees of polarity, flexibility, and reactivity.
View Article and Find Full Text PDFJ Org Chem
November 2024
College of Pharmacy, National & Local Joint Engineering Research Center of Targeted and Innovative Therapeutics, IATTI, Chongqing University of Arts and Sciences, Chongqing 402160, China.
Sulfonylhydrazones have been proven to be versatile synthetic intermediates in a panel of transformations. However, radical sulfonylation with sulfonylhydrazone as sulfonyl radical source is relatively rare. Here, we found that sulfonylhydrazone can serve as a new sulfonyl radical precursor to couple various partners such as arylacetic acids, ene-yne-ketones, and -quinone methides under copper catalysis and microwave irradiation.
View Article and Find Full Text PDFChemistry
December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, China, 330031.
After systematic realization of decarboxylative functionalization of carboxylic acids under heating conditions in our group, we herein reported an electrochemical method for Ni-catalyzed decarboxylative oxygenation of arylacetic acids under open air conditions. The protocol provided corresponding carbonyls including aldehydes and ketones in moderate to satisfactory yields with good functional group tolerance, furthermore, the practicability and advantage of the method was highlighted through Ni-catalyzed oxidative decarboxylation of carboxylic acid-containing drugs and preformation of scalable transformation. Mechanistic studies demonstrated that the possible involvement of free radical intermediate in the conversion.
View Article and Find Full Text PDFOrg Biomol Chem
July 2024
Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, China.
Angew Chem Int Ed Engl
July 2024
School of Chemical Science and Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, P.R. China.
A hitherto unknown class of C-symmetric C-C (C, C, C, C) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp)-H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2-hydroxymethyl-3-naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the C-symmetric α,α,α,α-atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C-H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity.
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