The first and facile synthesis of N,N'-dialkylated 2,6,9-triazabicyclo[3.3.1]nonadienes was achieved by the [4 + 4] self-condensation of β-formyl-β-nitroenamine in the presence of ammonium acetate. The 2,6- and 2,9-dialkylated products were found to be interconvertible when dissolved in a solvent. This isomerization proceeds through intramolecular ring transformation via a common intermediate under equilibrium.
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http://dx.doi.org/10.1039/d0ob01950j | DOI Listing |
Chemistry
January 2025
Osaka Metropolitan University: Osaka Koritsu Daigaku, Chemistry, 3-3-138 Sugimoto, Sumiyoshi-ku, 558-8585, Osaka, JAPAN.
Gold(I)-catalyzed intramolecular hydroarylation of dialkynyl(biaryl)phosphine oxides provided versatile benzo-fused phosphepine oxides. O-exo adducts were obtained as the major product, and O-endo adducts were the minor product. O-exo and O-endo indicate the position of an oxygen atom with respect to the central phosphepine framework.
View Article and Find Full Text PDFChemistry
January 2025
Indian Institute of Technology Madras, Department of Chemistry, Chennai, Chennai, INDIA.
A series of significantly bulky mono- and di-substituted cyclic alkyl-amino carbene (cAAC)- functionalized cyclopentadiene ring (Cp) compounds were synthesized. The functionalization of the Cp ring with cAAC ligands makes them significantly bulkier, while retaining their ligation properties. These compounds display interesting fluorescence properties.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, School of Environment, South China Normal University, Guangzhou 510006, China.
Two-dimensional (2D) electronic spectra of the phenylene ethynylene dendrimer with 2-ring and 3-ring branches were evaluated by combining the on-the-fly trajectory surface hopping nonadiabatic dynamics and the doorway-window simulation protocol. The ground state bleach (GSB), stimulated emission (SE), and excited-state absorption (ESA) contributions to the 2D signal were obtained and carefully analyzed. The results demonstrate that the ultrafast intramolecular nonadiabatic excited-state energy transfer (EET) from the 2-ring to the 3-ring units is comprehensively characterized by the SE and ESA signals.
View Article and Find Full Text PDFJ Org Chem
January 2025
School of Pharmacy, Hangzhou Medical College, 8 Yikang Road, Hangzhou 311300, PR China.
A Fe-catalyzed hydrocyclization reaction of unactivated alkenes was developed, utilizing PhSiH as the hydrogen source, yielding 2,3-dihydroquinazolinone (DHQZ) derivatives in moderate to good yields. Notably, when the substrate was switched to -cyano--(2-(prop-1-en-2-yl)phenyl)benzamides, the reaction yielded only the unreduced products. Mechanistic studies revealed that the intramolecular addition of the in situ formed radical to the unactivated alkene results in the formation of the fused ring.
View Article and Find Full Text PDFChemistry
January 2025
TU Chemnitz: Technische Universitat Chemnitz, Insitut für Chemie, Straße der Nationen 62, 09111, Chemnitz, GERMANY.
The intramolecular migration of three hydrogen atoms from one moiety of a gaseous radical cation to the other prior to fragmentation is an extremely rare type of redox reaction. Within the scope of this investigation, this scenario requires an ionized but electron-rich arene acceptor bearing a para-(3-hydroxyalkyl) residue. The precise mechanism of such unidirectional 3H transfer processes, including the order of the individual H transfer steps, has remained unclear in spite of previous isotope labelling and recent infrared ion spectroscopy (IRIS) studies.
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