Interest in stable nucleophilic carbenes has grown rapidly since the isolation of the first "bottle-able" example in 1991. Not only has the structural variation of this class of compounds seen an incredible expansion from laboratories around the world, but the chemical reactivity of these compounds has opened many new opportunities for improvements in chemical transformations and invention of new processes. This article reflects our particular interest in fused polycyclic carbenes and focuses on this broad chemical class from both a structural and reactivity perspective.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/b907211j | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Insight into the Excited States in Monomers and π-Stacked Dimers of Azulene-Fused Acenes: ADC(2) and TD-DFT Studies.
J Phys Chem A
January 2025
Department of Chemistry, Indian Institute of Technology, Guwahati 781039, India.
Charge transfer (CT) states in polycyclic aromatic hydrocarbons play crucial roles in determining their electronic properties and their potential applications in organic electronics. In this work, we investigate the nature of the excited states in monomers and π-stacked dimers of azulene-fused naphthalene and anthracene systems, focusing on the interplay between structure and excited-state properties. Four different isomers for azulene-fused naphthalene (, , , and ) and anthracene (, , , and ) are considered.
View Article and Find Full Text PDFManipulating Crystal Packing and Self-Assembly by π-Extended and Isomeric Fused Strategies in Thiophene Ring-Terminated Polycyclic Aromatic Hydrocarbons.
Org Lett
January 2025
Department of Materials Science, State Key Laboratory of Molecular Engineering of Polymers, Laboratory of Molecular Materials and Devices, Fudan University, Shanghai 200433, China.
Two series of polycyclic aromatic hydrocarbon isomers ( and , and and ) were designed and synthesized by isomerically fusing phenanthrene with thiophene and thieno[3,2-]thiophene, respectively. All of the new target molecules were confirmed by single-crystal X-ray analysis, and it was found that the solid-state packing can be effectively modulated through a combination of π-extended and isomeric fused strategies. Meanwhile, compared with thiophene ring-terminated isomers and , both having a V-shaped geometry and showing no obvious self-assembly behavior, π-extended unit thieno[3,2-]thiophene-terminated isomer displays a V-shaped structure with moderate self-assembly properties and isomer exhibits a C-shaped configuration with further enhanced self-assembly properties.
View Article and Find Full Text PDFGround and excited state aromaticity in azulene-based helicenes.
Chemphyschem
January 2025
Institute of Molecular Science Marseille, Département de chimie, FRANCE.
Electron delocalization is studied in the ground singlet and first excited triplet states of azulene-containing helicenes. After showing that the compounds we study can be synthesized, we show that they exhibit a charge separation in the ground state, which does not appear in their triplet excited state. Then, magnetically induced properties (IMS3D and ACID) and electron density decomposition methods (EDDB) are used to rationalize aromaticity in these systems.
View Article and Find Full Text PDFSelective and Divergent Synthesis of Naphthalene- and Phenanthrene-Fused Azahelicenes by Turning Rearrangement On or Off.
Chemistry
January 2025
Okayama Daigaku Daigakuin Shizen Kagaku Kenkyuka, Division of Applied Chemistry, JAPAN.
The Scholl reaction has been used to synthesize a variety of polycyclic aromatic hydrocarbons, where 1,2-aryl shifts have sometimes occurred to yield unique rearrangement products. However, such 1,2-aryl shifts are often uncontrollable, and the selective and divergent synthesis with or without rearrangement is desired. Here, we achieved the control of the rearrangement in the Scholl reaction of carbazoles by the N-substituents.
View Article and Find Full Text PDFPalladium-Catalyzed Tandem Reactions via Allene Intermediates for the Rapid Synthesis of a Fused Indenone-Indole Scaffold.
Org Lett
January 2025
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211800, China.
A palladium-catalyzed tandem reaction of 1-(2-iodophenyl)-3-arylprop-2-yn-1-ones and 1-(2-azidophenyl)propargyl ethers is developed to provide the rapid construction of a fused polycyclic indenone-indole scaffold under mild conditions. The reaction proceeds via a highly ordered process involving Sonogashira coupling, propargyl-allenyl isomerization, allene-azide cycloaddition, denitrogenation, and diradical coupling. The proposed reaction mechanism is supported by experimental and computational studies.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!