A click end-capping reaction exploiting nitrile N-oxide to rotaxane was described with emphasis of productivity of the protocol via stable C-C bond formation. Establishment of a pH-driven molecular shuttling system was also demonstrated by practical neutralization of the sec-ammonium group of the rotaxane axle with potassium hydroxide.
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http://dx.doi.org/10.1021/ol101543x | DOI Listing |
Anal Chem
January 2025
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
This study tackles the challenge of enantiodifferentiation of nitrile compounds, which is typically difficult to resolve using nuclear magnetic resonance (NMR) due to the significant distance between the chiral center and the nitrogen atom involved in molecular interactions. We have developed novel chiral F-labeled probes, each featuring two chiral centers, to exploit the "match-mismatch" effect, thereby enhancing enantiodiscrimination. This strategy effectively differentiates chiral analytes with quaternary chiral carbon centers as well as those with similar substituents at the chiral center.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Radiology, Molecular Imaging Program at Stanford, Stanford University School of Medicine, Stanford, California 94305, United States.
Accumulation of misfolded proteins challenges cellular proteostasis and is implicated in aging and chronic disorders. Cancer cells, moreover, face an elevated level of basal proteotoxic stress; hence, exacerbating endoplasmic reticulum (ER) stress has been shown to induce programmed cell death while enhancing anticancer immunogenicity. We hypothesize that hydrophobic abiotic macromolecules can trigger a similar stress response.
View Article and Find Full Text PDFOrg Lett
December 2024
School of Chemistry, University College Dublin, O'Brien Centre for Science, Belfield, Dublin 4, Ireland.
Continuous flow technology was exploited for the effective generation of nitrile imines via photolysis of substituted aryl tetrazoles. The resulting photo-click process rapidly affords advanced nitrogen-rich scaffolds upon the subsequent trapping of the reactive dipole with alkenes, alkynes, and benzylic amines. Crucially, this approach uncovers the differential reactivity for ether vs amine tethers, thus providing facile and scalable access to underexplored medicinally relevant heterocyclic entities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
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.
View Article and Find Full Text PDFJ Phys Chem B
November 2024
Institut für Chemie, Sekr. PC14, Technische Universität Berlin, Straße des 17. Juni 135, Berlin D-10623, Germany.
A profound understanding of protein structure and mechanism requires dedicated experimental and theoretical tools to elucidate electrostatic and hydrogen bonding interactions in proteins. In this work, we employed an approach to disentangle noncovalent and hydrogen-bonding electric field changes during the reaction cascade of a multidomain protein, i.e.
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