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1,4-Phenylene-linked cyclotrimer () and cyclotetramer () have been synthesized via Lewis acid-catalyzed self-condensation of appropriate precursors. Structural and Density Functional Theory (DFT) studies reveal the disruption of annulenic conjugation in both and by linking phenylene rings prevented them from global antiaromaticity. The single crystal X-ray structure of reveals all the nitrogens are pointing toward the macrocyclic core with near-planar and square-shaped geometry, thus in sharp contrast to the ring-strained conformation of .
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http://dx.doi.org/10.1021/acs.orglett.1c03903 | DOI Listing |
J Am Chem Soc
August 2025
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.
The tungsten fragment {WTp(NO)(PMe)} (Tp = trispyrazolylborate) is an effective dearomatization agent for benzene and its derivatives. The dihapto-coordination of this system to an arene disrupts its aromatic stability, thereby promoting facile electrophilic additions to the hydrocarbon, which can then be followed by the addition of nucleophiles. This preliminary study endeavors to extend this conceptual approach to other aromatic and antiaromatic carbocycles.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
State Key Laboratory of Advanced Materials for Intelligent Sensing and Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin University, No. 92 W
The comprehensive understanding of the ground-state electronic structures of all-benzenoid macrocycles and their charged species, particularly those exhibiting global (anti)aromaticity, remains poorly resolved. Here, we present two imine- and methine-bridged all-benzenoid [6]cyclo-para-phenylenes SPAZ (superpyrazine) and STAZ (supertriazine)-designed as π-extended analogues of 1,4-pyrazine and 1,3,5-triazine, respectively. For the first time, we elucidate their unprecedented valence tautomerism between "super-Kekulé" alternating benzenoid/quinoidal structures and a "super-sextet" transient structure, mediated by a 30π azaannulene conjugated pathway.
View Article and Find Full Text PDFComb Chem High Throughput Screen
January 2025
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran.
Aims: This study aims explore the impact of catechol, dopamine, and L-DOPA on the stability and toxicity of β-amyloid peptides, which play a key role in the neurodegenerative process of Alzheimer's disease, to assess their potential as therapeutic agents.
Background: Alzheimer's disease is marked by the aggregation of β-amyloid peptides, which contribute to neurodegeneration. Exploring how various compounds interact with β-amyloid peptides can offer valuable insights into potential therapeutic strategies.
Nanoscale
January 2023
Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic.
Fully aromatic helicenes are attractive building blocks for the construction of inherently chiral π-conjugated macrocyclic nanocarbons. These hitherto rare molecular architectures are envisaged to exhibit remarkable (chir)optical properties, self-assembly, charge/spin transport, induced ring current or a fascinating Möbius topology. Here the synthesis of helically chiral macrocycles that combine angular dibenzo[5]helicene units as corners and linear -stilbene-4,4'-diyl linkers as edges is reported.
View Article and Find Full Text PDFOrg Lett
January 2022
Indian Institute of Science Education and Research Thiruvananthapuram, Kerala 695 016, India.
1,4-Phenylene-linked cyclotrimer () and cyclotetramer () have been synthesized via Lewis acid-catalyzed self-condensation of appropriate precursors. Structural and Density Functional Theory (DFT) studies reveal the disruption of annulenic conjugation in both and by linking phenylene rings prevented them from global antiaromaticity. The single crystal X-ray structure of reveals all the nitrogens are pointing toward the macrocyclic core with near-planar and square-shaped geometry, thus in sharp contrast to the ring-strained conformation of .
View Article and Find Full Text PDF