Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• pyrrolidine at 0 °C, the pentafulvene derivative 36 was obtained with 63% yield via an additional ring-opening process. Similar skeletal transformation reactions were observed for azulene derivatives bearing similar substructures. The reaction of 1 with TCNE in an aqueous medium containing a surfactant

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• helical NG 44 containing [6]helicene structure and an azulene unit (Scheme 5). Through a two-fold Diels–Alder cycloaddition from 1,4-bis(2-ethynylphenyl)buta-1,3-diyne (41) and tetracyclone 11, alkyne 42 was obtained in an 83% yield. Then unique diiodide precursor 43 was obtained by ICl-mediated

Germacrene B – a central intermediate in sesquiterpene biosynthesis

• Houchao Xu and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 186–203, doi:10.3762/bjoc.19.18

• ., by heating with sulphur, to the blue azulene derivative 62 (Scheme 16C) [121][122][124][125][126], but the structure elucidation of this compound was only completed in 1936 [127]. Based on a comparison of IR spectra of natural terpenes, their hydrogenation and dehydrogenation products, the correct

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• Vijayendra S. Shetti Department of Chemistry, National Institute of Technology Karnataka, Surathkal 575025, India 10.3762/bjoc.17.139 Abstract Azulene is a non-alternant, aromatic hydrocarbon with many exciting characteristics such as having a dipole moment, bright color, stimuli responsiveness

• , anti-Kasha photophysics, and a small HOMO–LUMO gap when compared to its isomer, naphthalene. These properties make azulene-containing polymers an intriguing entity in the field of functional polymers, especially for organic electronic applications like organic field-effect transistors (OFET) and

• photovoltaic (PV) cells. Since azulene has a fused five and seven-membered ring structure, it can be incorporated onto the polymer backbone through either of these rings or by involving both the rings. These azulene-connection patterns can influence the properties of the resulting polymers and the chemical

Switchable selectivity in Pd-catalyzed [3 + 2] annulations of γ-oxy-2-cycloalkenones with 3-oxoglutarates: C–C/C–C vs C–C/O–C bond formation

• Yang Liu,
• Julie Oble and
• Giovanni Poli

Beilstein J. Org. Chem. 2019, 15, 1107–1115, doi:10.3762/bjoc.15.107

• combination may allow direct access to either fused bicyclic cyclopentanic (pentalene-, indene-, or azulene-type) structures via a γ-C-allylation/β-C-1,4 addition process, or annulated furan-based motifs through a γ-C-allylation/β-O-1,4 addition process, both motifs being incorporated into biologically

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• by NMR as well as other spectroscopic techniques. Georghiou et al. demonstrated the mechanochemical formation of a 1:1 supramolecular complex C60–tert-butylcalix[4]azulene 41 (Figure 23). The host–guest complexation was achieved by simple grinding the individual compounds in a mortar and pestle [95

• –tert-butylcalix[4]azulene through mortar and pestle grinding of the host and the guest. The structure of the complex was obtained from DFT study. Formation of a 2:2 complex between the supramolecular catalyst and the reagent in the transition state of the [2 + 2]-cycloaddition reaction of 1,2-di

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

• Paris E. Georghiou,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Hidetaka Nishimura,
• Jaehyun Lee,
• Atsushi Wakamiya and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2018, 14, 2488–2494, doi:10.3762/bjoc.14.225

• USA 10.3762/bjoc.14.225 Abstract Some of the least studied calixarenes are those that consist of azulene rings bridged by -CH2- groups. Since Lash and Colby’s discovery of a simple and convenient method for producing the parent all-hydrocarbon calix[4]azulene, there have been two other all

• -hydrocarbon calix[4]azulenes which have been synthesized in good yields by their method. This allowed studying their supramolecular properties. This report is of our latest work on the solution-state supramolecular complexation of one of these calix[4]azulenes, namely tetrakis(5,7-diphenyl)calix[4]azulene or

• investigated. Keywords: azulene; calixarenes; calixazulenes; supramolecular chemistry; tetraalkylammonium salts; Introduction Among the great variety of synthetic macrocyclic molecular receptors which have been reported, those that are referred to by their generic name “calixarene” loom large [1][2][3]. The

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• arenes react well and substituted pyrroles and indoles give the corresponding sulfoxides in high yields. Less electron-rich thiophene or benzene derivatives gave low yields. Nevertheless, carbocyclic azulene afforded the respective sulfoxide in 88% yield. We propose an electrophilic aromatic substitution

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• steps, which can only be explained on the basis of the redox behavior of the azulene unit. The ability of the 4′-azulenyl 2,2′:6′,2″-terpyridine to bind poisoning metal cations was studied by UV–vis titrations using aqueous solutions of Hg(II) and Cd(II) chlorides as illustrative examples. Keywords

• : azulene; fluorescence; metal binding; synthesis; terpyridine; Introduction 2,2′:6′,2″-Terpyridine derivatives are extensively used organic ligands in the field of supramolecular chemistry and materials science [1][2][3][4]. Besides the interesting supramolecular architectures, metal–terpyridine complexes

• remarkable optical and redox properties, azulene proved to be an excellent building block for developing a large variety of materials ranging from NLO chromophores [13] to molecular switches [14][15] and liquid crystals [16] or high-conductance materials [17]. In contrast to most aromatic compounds which

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• synthesis of polyunsaturated [10]paracyclophane annulated by two azulene rings by using the McMurry reaction [100][101]. The bis(trimethylsilyl)enol ether 74 was reacted with 3-methoxycarbonyl-2H-cyclohepta[b]furan-2-one (75) in refluxing decaline to generate the 1,4-diazulenobenzene derivative 76. Double

• chain elongation of the bis-azulene derivative 76 with a four-carbon unit has been accomplished by electrophilic substitution with 4,4'-dimethoxybutan-2-one (77) under acidic conditions and subsequent elimination of methanol under basic conditions gave the advanced precursor 78 (28%). The

On the bromination of the dihydroazulene/vinylheptafulvene photo-/thermoswitch

• Virginia Mazzanti,
• Martina Cacciarini,
• Søren L. Broman,
• Christian R. Parker,
• Magnus Schau-Magnussen,
• Andrew D. Bond and
• Mogens B. Nielsen

Beilstein J. Org. Chem. 2012, 8, 958–966, doi:10.3762/bjoc.8.108

• a bromo substituent in the seven-membered ring. Conclusion: Two general procedures for functionalizing the DHA core with a bromo substituent (at positions 3 and 7, respectively) are now available with the DHA as starting material. Keywords: azulene; bromination; dihydroazulene; molecular switches

• started out with the 7-bromo-DHA 4. Treatment with bromine at −78 °C generated in this case, however, a very labile intermediate, tentatively assigned to the structure 13, which underwent ready conversion, without the addition of base, to the azulene 14 together with a complex mixture of other nonisolated

• not perform the controlled elimination of HBr by LiHMDS to generate the corresponding 7-bromo-DHA as we could from 3. The structure of the azulene 14 was confirmed by X-ray crystallographic analysis (Figure 3c). Functionalized azulenes are themselves interesting in materials chemistry for their

Synthesis of 2,6-disubstituted tetrahydroazulene derivatives

• Zakir Hussain,
• Henning Hopf,
• Khurshid Ayub and
• S. Holger Eichhorn

Beilstein J. Org. Chem. 2012, 8, 693–698, doi:10.3762/bjoc.8.77

• analysis of 8 revealed [22] an azulene framework that is partially hydrogenated to a cyclopentane subunit in places where molecules are slightly disordered in the lattice. These molecules represent the slightly torsionally distorted enantiomers of 8. At this stage we did not find any hydrogen atom at

One-pot four-component synthesis of pyrimidyl and pyrazolyl substituted azulenes by glyoxylation–decarbonylative alkynylation–cyclocondensation sequences

• Charlotte F. Gers,
• Julia Rosellen,
• Eugen Merkul and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2011, 7, 1173–1181, doi:10.3762/bjoc.7.136

• - and pyrazolylazulenes through the use of glyoxylation–decarbonylative alkynylation–cyclocondensation sequences starting from azulene or guaiazulene as substrates, gives rise to the formation of the target compounds in moderate to good yields. Keywords: azulenes; catalysis; decarbonylation

• these intermediates into many classes of heterocycles [12][13][14][15]. These novel MCRs nicely correspond with diversity-oriented strategies towards functional organic chromophores [1][2]. The striking blue color of azulene (1a) (from the Spanish word “azul” = blue) has aroused scientific attention for

• elucidation of the structure and the first synthesis of the azulene skeleton by Pfau and Plattner [21][22], its reactivity has been intensively studied [23][24][25][26]. The aromatic system is susceptible to nucleophilic addition in the 4-, 6- and 8-positions [23], whereas electrophilic aromatic substitution

Gold-catalyzed propargylic substitutions: Scope and synthetic developments

• Olivier Debleds,
• Eric Gayon,
• Emmanuel Vrancken and
• Jean-Marc Campagne

Beilstein J. Org. Chem. 2011, 7, 866–877, doi:10.3762/bjoc.7.99

• , alcohols, thiols, electron rich aromatic compounds), and showed that gold probably acts as a Lewis acid to promote the formation of a stabilized propargylic carbocation intermediate [23][24]. A related reaction was subsequently reported by Dyker [25] in 2006, using azulene and 1,3-dimethoxybenzene in