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1.
Yi Han Zibo Xue Dr. Guangwu Li Dr. Yanwei Gu Dr. Yong Ni Dr. Shaoqiang Dong Prof. Chunyan Chi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9111-9116
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials. 相似文献
2.
Yi Han Zibo Xue Guangwu Li Yanwei Gu Yong Ni Shaoqiang Dong Chunyan Chi 《Angewandte Chemie (International ed. in English)》2020,59(23):9026-9031
Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyloxylated product were obtained, as confirmed by X‐ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring‐fused substructure containing two formal azulene units is formed, but only one of them shows an azulene‐like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2‐phenyl migration and a naphthalene to azulene rearrangement reaction according to an in‐silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene‐based molecular materials. 相似文献
3.
[6+4] Cycloaddition reactions of functionalized thiophene dioxides with various fulvenes provided the corresponding azulenes.
The observed regiochemistry was explained in terms of the HOMO—LUMO orbital coefficients.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 137–142, January, 2006. 相似文献
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Neha Rani Kumar Abhijeet R. Agrawal Dr. Sanjio S. Zade 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14064-14071
Azulene is a non-alternant non-benzenoid aromatic system, and in turn, it possesses unusual photophysical properties. Azulene-based conjugated systems have received increasing interest in recent years as optoelectronic materials. Despite the routes available for the preparation of substituted azulene derivatives, there remain few methods that allow regioselective substitution on the seven-membered ring of azulenes due to the subtle reactivity difference among the various positions. This report explores the reactivity of substituted tropolones as the azulene precursors and also provides a new method to create 5-substituted azulenes. The reaction of cyanoacetate enolate with unsubstituted 2-methoxytropone affords azulene through the attack of the nucleophile on the C-2 center (normal pathway). We have observed that 3-substituted 2-methoxytropones undergo steric-guided nucleophilic addition at the C-7 center (abnormal pathway) to afford 5-substituted azulene derivatives. Based on this observation and DFT calculation, a new synthetic strategy is devised for the regioselective synthesis of 5-substituted multifunctional azulenes, which cannot be accessed by any other method. 相似文献
6.
Metal‐Catalyzed C−H Bond Activation of 5‐Membered Carbocyclic Rings: A Powerful Access to Azulene,Acenaphthylene and Fulvene Derivatives 下载免费PDF全文
Azulene, acenaphthylene and fulvene derivatives exhibit important physical properties useful in materials chemistry as well as valuable biological properties. Since about two decades ago, the metal‐catalyzed functionalization of such compounds, via C?H bond activation of their 5‐membered carbocyclic ring, proved to be a very convenient method for the synthesis of a wide variety of azulene, acenaphthylene and fulvene derivatives. For such reactions, there is no need to prefunctionalize the 5‐membered carbocyclic rings. In this review, the progress in the synthesis of azulene, acenaphthylene and fulvene derivatives via metal‐catalyzed C?H bond activation of their 5‐membered carbocyclic ring are summarized. 相似文献
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Paul Cowper Yu Jin Michael D. Turton Dr. Gabriele Kociok‐Köhn Dr. Simon E. Lewis 《Angewandte Chemie (International ed. in English)》2016,55(7):2564-2568
Azulenesulfonium salts may be readily prepared from the corresponding azulenes by an SEAr reaction. These azulene sulfonium salts are bench‐stable species that may be employed as pseudohalides for cross‐coupling. Specifically, their application in Suzuki–Miyaura reactions has been demonstrated with a diverse selection of coupling partners. These azulenesulfonium salts possess significant advantages in comparison with the corresponding azulenyl halides, which are known to be unstable and difficult to prepare in pure form. 相似文献
9.
A novel dicyanoheptafulvene 9 annulated by two spiro[4,5]deca-1,3-dienes was synthesized by the reaction of dispirocyclopentaazulenium cation 8 with bromomalononitrile. Although 9 was found to have a nonplanar heptafulvene structure by its X-ray crystallographic analysis, it is still capable of π-conjugation and thus shows appreciable contribution of the dipolar resonance form 9B based on its spectroscopic data. The degree of the contribution was further evaluated for various dicyanoheptafulvenes in terms of the partial sum of atomic charges of the dicyanomethylene group in the calculated structures besides the interplanar angles of the heptafulvene part and the length of the exocyclic double bond in the crystal structures. 相似文献
10.
Verónica A. Jiménez 《Structural chemistry》2009,20(4):677-684
Computational calculations at B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels were employed to analyze the structure and
conformation of 1,3-bis(4-bromophenyl)azulene (1), 1,3-bis(2-thienyl)azulene (2), and 1,3-bis(2-pyrrollyl)azulene (3) in order to rationalize the out-of-plane deformation found in the azulene cores of 1 and 2 in the crystalline state, whereas compound 3 shows a totally planar azulene moiety. Our results indicate that 1,3-disubstituted azulenes possess two almost equally stable
and easily convertible minimum energy conformers, which differ in the relative orientation of the substituent groups and in
the planarity degree of the azulene core. An absolute planarity index (P) is introduced to quantify the out-of-plane distortion found in the azulenes under study. The aromaticity of minimum energy
conformers was evaluated by means of geometric (HOMA), magnetic (NICS), and energetic (the frequency of the lowest out-of-plane
vibration, νmin) aromaticity indicators, which suggest that compound 3 possesses the most aromatic azulene core within the group. Calculated molecular dipole moments suggest that the conformation
of 1,3-disubstituted azulenes in the crystalline state can be explained in terms of electrostatic intermolecular interactions
rather than relative stability of planar and non-planar conformers. 相似文献