234-41-3Relevant academic research and scientific papers
Enhancing the Antiaromaticity ofs-Indacene through Naphthothiophene Fusion
Warren, Gabrielle I.,Barker, Joshua E.,Zakharov, Lev N.,Haley, Michael M.
, p. 5012 - 5017 (2021)
Addressing the instability of antiaromatic compounds often involves protection with bulky groups and/or fusion of aromatic rings, thus decreasing paratropicity. We report four naphthothiophene-fuseds-indacene isomers, one of which is more antiaromatic tha
Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials
Bin, Zhengyang,Liao, Xingrong,Liu, Jiahui,Shen, Boming,Shi, Yang,Yan, Lipeng,Yang, Feng,Yang, Ge,Yang, Yudong,You, Jingsong,Yu, Peiyuan
supporting information, (2021/12/14)
The installation of (benzo)thiophene-containing biaryls via coupling reactions has become a staple in designing photoelectric materials. Undeniably, C-H/C-H cross-coupling reactions between two (hetero)aromatics would be a shortcut toward these structural fragments. While more reliable cross-coupling technologies are well-established to provide C2-arylated (benzo)thiophenes, efficient methods that arylate the C3-position remain underdeveloped. Herein we provide insight into the factors that determine regioselectivity switching for these cross-coupling reactions. X-ray crystallographic analysis gives solid evidence for the key roles of triflate in regioselective dearomatization and acetate in base-assisted anti-β-deprotonated rearomatization. The first isolation and X-ray characterization of a medium-sized dearomatized cyclometalated adduct involving both substrates provide extra insight into aerobic oxidative Ar-H/Ar-H cross-coupling reactions. The mechanistic breakthrough incubates the first example, enabling C-H/C-H-type C3-arylation of benzothiophenes. Finally, this chemistry is used to design blue-emitting thermally activated delayed fluorescence (TADF) materials with a helicene conformation that exhibit a high maximum external quantum efficiency of 25.4% in OLED.
Method for synthesizing phenanthrene and derivatives thereof
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Paragraph 0084-0095, (2019/03/26)
The present invention provides a method for synthesizing phenanthrene and derivatives thereof represented by a formula (III) or (IV). The method is characterized in that a substituted 2-phenylcinnamaldehyde compound represented by a formula (I) or 2-thiophenylcinnamaldehyde represented by a formula (II) is taken as an initial substance, under the effect of a silver catalyst, an oxidant, a basic substance and a solvent, a reaction is carried out at 60 DEG C-100 DEG C for 12-36 hours, the reaction solution is separated and purification is carried out, so that corresponding phenanthrene and derivatives thereof represented by the formula (III) or (IV) are obtained. The synthesis method of the invention has the characteristics of small environmental hazard, mild reaction conditions, simple operation and the like.
Method for synthesizing phenanthrene compound by using nitroolefin
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Paragraph 0081-0084; 0085-0088; 0089-0092, (2019/03/26)
The invention provides a method for synthesizing a phenanthrene compound. According to the synthesizing method, a 2-phenyl nitroolefin compound as shown in a formula (I) or a 2-thienyl nitroolefin asshown in the formula (II) is used as an initiator for carrying out a reaction at a temperature of 60-100 DEG C for 4-12 hours under the action of an alkaline substance, a silver catalyst, an oxidizingagent and a solvent, and then the corresponding phenanthrene compound as shown in a formula (III) or a formula (IV) is prepared through separation and purification of a reaction liquid. The synthesizing method disclosed by the invention has the characteristics of small harm to the environment, mild reaction conditions, simple and convenient operation, and the like.
Synthetic Utility of Arylmethylsulfones: Annulative π-Extension of Aromatics and Hetero-aromatics Involving Pd(0)-Catalyzed Heck Coupling Reactions
Sankar, Elumalai,Raju, Potharaju,Karunakaran, Jayachandran,Mohanakrishnan, Arasambattu K.
, p. 13583 - 13593 (2017/12/26)
A straightforward and general method for the synthesis of annulated thiophene, dibenzothiophene, and carbazoles analogues has been achieved involving alkylation of 2-bromo-1-(phenylsulfonylmethyl)arene/heteroarene with arylmethyl bromides/heteroarylmethyl bromides using t-BuOK as a base in DMF, followed by Pd(0)-mediated intramolecular Heck coupling in the presence of K2CO3 in DMF at 80-140 °C. The attractive feature of this protocol is that a wide variety of π-conjugated heterocycles could be readily accessed by an appropriate choice of arylmethylsulfones and benzylic bromides.
A combined experimental and computational study on the cycloisomerization of 2-ethynylbiaryls catalyzed by dicationic arene ruthenium complexes
Yamamoto, Yoshihiko,Matsui, Kazuma,Shibuya, Masatoshi
supporting information, p. 7245 - 7255 (2015/05/05)
Ruthenium-catalyzed cycloisomerization of 2-ethynylbiaryls was investigated to identify an optimal ruthenium catalyst system. A combination of [η6-(p-cymene)RuCl2(PR3)] and two equivalents of AgPF6 effectively converted 2-ethynylbiphenyls into phenanthrenes in chlorobenzene at 120 °C over 20 h. Moreover, 2-ethynylheterobiaryls were found to be favorable substrates for this ruthenium catalysis, thus achieving the cycloisomerization of previously unused heterocyclic substrates. Moreover, several control experiments and DFT calculations of model complexes were performed to propose a plausible reaction mechanism.
Base-Promoted/Gold-Catalyzed Intramolecular Highly Selective and Controllable Detosylative Cyclization
Zhu, Chenghao,Qiu, Lin,Xu, Guangyang,Li, Jian,Sun, Jiangtao
supporting information, p. 12871 - 12875 (2015/09/07)
A highly selective, controllable and synthetically useful base-promoted intramolecular detosylative cyclization of bis-N-tosylhydrazones has been achieved, affording N-containing heterocycles and cyclic olefins under transition-metal-free or gold-catalyzed procedures, respectively. Moreover, an effective and practical metal-free or gold-catalyzed approach to synthesize polycyclic aromatic compounds is also reported. Basic cyclizations: A highly selective, controllable, and synthetically useful base-promoted intramolecular detosylative cyclization of bis-N-tosylhydrazones affords N-containing heterocycles and cyclic olefins under transition-metal-free or gold-catalyzed procedures, respectively. Moreover, an effective and practical metal-free or gold-catalyzed approach to synthesize polycyclic aromatic compounds is also reported.
Bismuth-catalyzed synthesis of polycyclic aromatic hydrocarbons (PAHs) with a phenanthrene backbone via cyclization and aromatization of 2-(2-arylphenyl)vinyl ethers
Murai, Masahito,Hosokawa, Naoki,Roy, David,Takai, Kazuhiko
supporting information, p. 4134 - 4137 (2014/09/30)
The reaction of 2-(2-arylphenyl)vinyl ethers in the presence of a catalytic amount of bismuth(III) triflate gave substituted phenanthrenes in excellent yields under mild reaction conditions. The reaction was also applied to the construction of other polycyclic aromatic hydrocarbons (PAHs), such as chrysene, helicene, and pyrene having a phenanthrene backbone, via regioselective cyclization. This method has the advantages of easy availability of the cyclization precursors, operational simplicity, and high reaction efficiency.
Synthesis of phenanthrenes by cationic chromium(III) porphyrin-catalyzed dehydration cycloaromatization
Wakabayashi, Ryota,Kurahashi, Takuya,Matsubara, Seijiro
supporting information, p. 2297 - 2301 (2013/11/06)
Readily available biphenyl derivatives with ortho oxirane moiety react in the presence of cationic chromiun(III) porphyrin catalyst to afford phenanthrenes. The reaction is considered to be triggered by activation of the oxirane moiety through coordination to the Lewis acidic cationic chromium to give aldehyde via 1,2-hydride shift, which reacts with arene through intramolecular electrophilic aromatic substitution and subsequent dehydration. The reaction allows constructing a variety of polycyclic aromatic and heteroaromatic compounds.
A facile two-step synthesis of thiophene end-capped aromatic systems
Rungtaweevoranit, Bunyarat,Butsuri, Akkarapol,Wongma, Krittaphat,Sadorn, Karoon,Neranon, Kitjanit,Nerungsi, Chakkrapan,Thongpanchang, Tienthong
supporting information; experimental part, p. 1816 - 1818 (2012/05/05)
Thiophene end-capped aromatic analogues, that is, naphthothiophenes, naphthodithiophenes, pyrenothiophene, and benzotrithiophene, can be prepared from commercially available hydroxyarenes in two steps, including (1) a consecutive acid-mediated nucleophilic aromatic substitution of hydroxyarenes with 2-mercaptoethanol, followed by cyclization to form an arene-fused dihydrothiophene, and (2) oxidation of the dihydrothiophene unit to thiophene.
