- Palladium-catalyzed carbopalladation and carbocyclization of arynes with aryl halides: A highly efficient route to functionalized triphenylenes
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Highly substituted triphenylene derivatives were prepared in good yields via the palladium-catalyzed carbocyclization of arynes with aryl iodides. The Royal Society of Chemistry 2006.
- Jayanth, Thiruvellore Thatai,Cheng, Chien-Hong
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- Synthesis of fused polycyclic aromatics by palladium-catalyzed annulation of arynes using 2-halobiaryls
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The Pd-catalyzed annulation of arynes by 2-halobiaryls and related vinylic halides provides a very efficient, high yielding synthesis of polycyclic aromatic and heteroaromatic hydrocarbons. This process appears to involve the catalytic, stepwise coupling
- Liu, Zhijian,Zhang, Xiaoxia,Larock, Richard C.
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- Atmosphere-Controlled Palladium-Catalyzed Divergent Decarboxylative Cyclization of 2-Iodobiphenyls and α-Oxocarboxylic Acids
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A novel palladium-catalyzed divergent decarboxylative cyclization of 2-iodobiphenyls and α-oxocarboxylic acids utilizing the atmosphere as a controlled switch is reported. Under the protection of a nitrogen atmosphere, tribenzotropones are synthesized by a [4 + 3] decarboxylative cyclization. Employing a palladium/O2 system enables a [4 + 2] decarboxylative cyclization to assemble triphenylenes. Notably, preliminary mechanistic studies indicate that the formation of triphenylenes involves a double decarboxylation.
- Zhou, Liwei,Sun, Mingjie,Zhou, Fengru,Deng, Guobo,Yang, Yuan,Liang, Yun
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p. 7150 - 7155
(2021/09/18)
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- Two-in-One Strategy for the Pd(II)-Catalyzed Tandem C-H Arylation/Decarboxylative Annulation Involved with Cyclic Diaryliodonium Salts
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We report here a two-in-one strategy for the Pd(II)-catalyzed tandem C-H arylation/decarboxylative annulation between readily available cyclic diaryliodonium salts and benzoic acids. The carboxylic acid functionality can be used as both a directing group for the ortho-C-H arylation and the reactive group for the tandem decarboxylative annulation. By a step-economical double cross-coupling annulation procedure, the privileged triphenylene frameworks were efficiently constructed, which have potential applications in material chemistry.
- Hu, Tao,Xu, Kai,Ye, Zenghui,Zhu, Kai,Wu, Yanqi,Zhang, Fengzhi
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supporting information
p. 7233 - 7237
(2019/10/02)
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- Synthesis of triphenylene derivatives by Pd-catalyzed Suzuki coupling/intramolecular C–H activation between arylboronic acids and dibromobiphenyls
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An efficient and regioselective synthesis of functionalized triphenylenes via palladium-catalyzed Suzuki-Miyaura coupling and subsequent intramolecular C–H activation between arylboronic acids and dibromobiphenyls was developed. This methodology showed excellent atomic economy and regiospecificity as well as synthetic feasibility of unsymmetrical triphenylenes.
- Tu, Jingxuan,Li, Gaoqiang,Zhao, Xiaoqian,Xu, Feng
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- Synthesis of Functionalized Triphenylenes via a Traceless Directing Group Strategy
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A novel ligand-free Pd-catalyzed cascade reaction between o-chlorobenzoic acids and cyclic diaryliodonium salts is reported. This one-pot procedure involves a carboxylic acid directed o-arylation followed by intramolecular decarboxylative annulation affording various valuable triphenylenes, which can be further transformed into diversified building blocks for material chemistry. For the first time, it was shown that an aromatic halide can react with diaryliodonium salts under the direction of carboxylic acid functionality. It was also demonstrated that the carboxylic acid could be employed as both a traceless directing group and functional handle for the atom- and step-economical one-pot double cross-coupling annulation reaction with cyclic diaryliodonium salts as the π-extending agents.
- Yang, Shuai,Wang, Feng,Wu, Yanqi,Hua, Wenkai,Zhang, Fengzhi
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supporting information
p. 1491 - 1495
(2018/03/23)
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- Palladium Catalyzed C-I and Vicinal C-H Dual Activation of Diaryliodonium Salts for Diarylations: Synthesis of Triphenylenes
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Using the synthetic strategy of palladium-catalyzed dual activation of both C-I and vicinal C-H bonds of diaryliodonium salts, we report an approach for direct diarylations of 2-bromobiphenyls or bromobenzenes. As a result, a wide range of triphenylenes with various substituents have been synthesized in good yields. These triphenylenes are expected to be employed in the "bottom-up" synthesis of functional aromatic molecules in material science.
- Wu, Xunshen,Han, Jianwei,Wang, Limin
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- Synthetic method for 9,10-benzophenanthrene compound
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The invention discloses a synthetic method for a 9,10-benzophenanthrene compound. The synthetic method comprises the following concrete steps: dissolving a compound as shown in a formula (2) which is described in the specification and another compound as shown in a formula (4) which is described in the specification in N,N-dimethyl formamide under the protection of inert gas; and carrying out a reaction at 120 to 140 DEG C under the action of copper trifluoromethanesulfonate, sodium carbonate and caesium acetate so as to obtain the 9,10-benzophenanthrene compound as shown in a formula (I) which is described in the specification. According to the invention, 2-bromobiphenyl is used as a raw material, diaryl iodate is used as an arylation reagent, bivalent copper is used as a catalyst, and sodium carbonate and caesium acetate are used as mixed base; the synthetic method has the characteristics of usage of easily available raw materials, short reaction time, high yield, etc.; and as a simplest graphene monomer, the synthesized 9,10-benzophenanthrene compound good application prospects in the field of organic photoelectricity.
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Paragraph 0061; 0062; 0064; 0065
(2018/01/09)
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- Method for synthesizing triphenylene compound
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The invention provides a method for synthesizing a triphenylene compound represented by a formula (III) shown in the description. The method comprises the steps: dissolving a benzoic acid compound represented by a formula (I) shown in the description, a cyclic iodine onium salt represented by a formula (II) shown in the description, palladium acetate and potassium carbonate in N-methyl pyrrolidone, heating the temperature of the solution to 110 DEG C to 145 DEG C, carrying out a reaction for 6 to 17 hours with stirring, then, subjecting the reacted solution to aftertreatment, thereby obtaining the triphenylene compound. According to the method, the reaction system is simple, the raw materials, particularly the benzoic acid compound are easily obtained, and a substrate is not required to be prepared by multiple steps, so that the reaction yield of the method is relatively high; and the triphenylene is obtained through a one-step reaction between the benzoic acid compound and the cyclic iodine onium salt, so that the reaction route is greatly shortened, and the yield of the obtained corresponding triphenylene compound is 93% to the maximum.
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Paragraph 0023; 0024; 0025; 0038; 0039; 0040
(2017/12/28)
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- C-C Bond (Hetero)arylation of Ring-Fused Benzocyclobutenols and Application in the Assembly of Polycyclic Aromatic Hydrocarbons
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Herein, we disclose a new and efficient synthetic approach to triphenylene-based polycyclic aromatic hydrocarbons (PAHs) from ring-fused benzocyclobutenols (RBCBs) through the cleavage of the C-C σ-bond. Two key transformations are involved: (a) palladium-catalyzed C-C bond (hetero)arylation of RBCBs; and (b) Lewis acid-promoted intramolecular annulation leading to complex polycyclic compounds. A variety of multiply substituted triphenylenes and derivatives are obtained in synthetically useful yields.
- Mao, Wenbin,Zhu, Chen
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p. 9133 - 9143
(2017/09/11)
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- Synthesis of Triphenylenes Starting from 2-Iodobiphenyls and Iodobenzenes via Palladium-Catalyzed Dual C-H Activation and Double C-C Bond Formation
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A novel and facile approach for the synthesis of triphenylenes has been developed via palladium-catalyzed coupling of 2-iodobiphenyls and iodobenzenes. The reaction involves dual palladium-catalyzed C-H activations and double palladium-catalyzed C-C bond formations. A range of unsymmetrically functionalized triphenylenes can be synthesized with the reaction. The approach features readily available starting materials, high atom- and step-economy, and access to various unsymmetrically functionalized triphenylenes.
- Zhang, Yanghui,Pan, Shulei,Jiang, Hang,Zhang, Yu,Chen, Dushen
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p. 5192 - 5195
(2016/11/02)
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- Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by Cascade Reaction of o-Iodobiphenyls or (Z)-β-Halostyrenes with o-Bromobenzyl Alcohols through Two Sequential C-C Bond Formations Catalyzed by a Palladium Complex
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o-Bromobenzyl alcohol has been developed as a novel annulating reagent, bearing both nucleophilic and electrophilic substituents, for the facile synthesis of polycyclic aromatic hydrocarbons. A palladium/electron-deficient phosphine catalyst efficiently coupled o-iodobiphenyls or (Z)-β-halostyrenes with o-bromobenzyl alcohols to afford triphenylenes and phenanthrenes, respectively. The present cascade reaction proceeded through deacetonative cross-coupling and sequential intramolecular cyclization. An array of experimental data suggest that the reaction mechanism involves the equilibrium of 1,4-palladium migration.
- Iwasaki, Masayuki,Araki, Yasuhiro,Iino, Shohei,Nishihara, Yasushi
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p. 9247 - 9263
(2015/09/28)
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- Palladium-catalyzed annulation of o-iodobiphenyls with o-bromobenzyl alcohols: Synthesis of functionalized triphenylenes via C-C and C-H bond cleavages
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Treatment of o-iodobiphenyls with o-bromobenzyl alcohols in the presence of cesium carbonate under palladium catalysis affords a series of highly substituted triphenylenes. The reaction involves two C-C bond formations and C-C and C-H bond cleavages. A combination of palladium and an electron-deficient phosphine ligand proves to be effective for both decarbonylative cross-coupling and intramolecular cyclization.
- Iwasaki, Masayuki,Iino, Shohei,Nishihara, Yasushi
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p. 5326 - 5329
(2013/11/06)
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- Highly efficient route to fused polycyclic aromatics via palladium-catalyzed aryne annulation by aryl halides
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Polycyclic aromatic and heteroaromatic hydrocarbons have been synthesized in high yield by two different processes involving the Pd-catalyzed annulation of arynes. The first process involves a Pd-catalyzed annulation of arynes by 2-halobiaryls and related vinylic halides. The second process utilizes a Pd-catalyzed double annulation of arynes by simple aryl halides. Both processes appear to involve the catalytic, stepwise coupling of two very reactive substrates, an aryne and an organopalladium species, to generate excellent yields of cross-coupled products.
- Liu, Zhijian,Larock, Richard C.
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p. 223 - 232
(2007/10/03)
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- Ambient measurement of nitrotriphenylenes and possibility of nitrotriphenylene formation by atmospheric reaction
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Environmental nitration of PAHs by nitrogen oxides on airborne particulates and identification and quantification of nitro-PAHs in them have been studied on fluoranthene and pyrene because of their large abundance. However, the direct mutagenic activity of these nitro-PAHs can account for only up to about 20% of the total direct mutagenic activity of airborne particulate samples, and the presence of unknown mutagenic nitro-PAHs was suggested. 1- and 2-Nitrotriphenylenes were first identified and quantified in ambient particulate samples collected in Tokyo. Their mutagenicity and formation by laboratory reactions of triphenylene deposited on a filter with NO2/NO3/N2O5 were also investigated. The concentrations of 1- and 2- nitrotriphenylenes were much higher than that of 1-nitropyrene in the same samples. 2-Nitrotriphenylene showed over 2 orders of magnitude greater mutagenic activity than 1-nitrotriphenylene in both strains TA98 and YG1024 (18 and 480 revertants/nmol for 1-nitrotriphenylene and 3800 and 101 700 revertants/nmol for 2-nitrotriphenylene in TA98 and YG1024). The mutagenic 2- nitrotriphenylene was expected to contribute largely to the total mutagenic activity of the extracts from airborne particulates. In addition, more effective formation of nitrotriphenylenes by the nighttime reaction of triphenylene in the presence of O3 in the dark can explain the observation of high nitrotriphenylene concentration in the nighttime samples. Environmental nitration of PAHs by nitrogen oxides on airborne particulates and identification and quantification of nitro-PAHs in them have been studied on fluoranthene and pyrene because of their large abundance. However, the direct mutagenic activity of these nitro-PAHs can account for only up to about 20% of the total direct mutagenic activity of airborne particulate samples, and the presence of unknown mutagenic nitro-PAHs was suggested. 1-and 2-Nitrotriphenylenes were first identified and quantified in ambient particulate samples collected in Tokyo. Their mutagenicity and formation by laboratory reactions of triphenylene deposited on a filter with NO2/NO3/N2O5 were also investigated. The concentrations of 1- and 2-nitrotriphenylenes were much higher than that of 1-nitropyrene in the same samples. 2-Nitrotriphenylene showed over 2 orders of magnitude greater mutagenic activity than 1-nitrotriphenylene in both strains TA98 and YG1024 (18 and 480 revertants/nmol for 1-nitrotriphenylene and 3800 and 101700 revertants/nmol for 2-nitrotriphenylene in TA98 and YG1024). The mutagenic 2-nitrotriphenylene was expected to contribute largely to the total mutagenic activity of the extracts from airborne particulates. In addition, more effective formation of nitrotriphenylenes by the nighttime reaction of triphenylene in the presence of O3 in the dark can explain the observation of high nitrotriphenylene concentration in the nighttime samples.
- Ishii, Satoko,Hisamatsu, Yoshiharu,Inazu, Koji,Kadoi, Morio,Aika, Ken-Ichi
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p. 1893 - 1899
(2007/10/03)
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- Chemistry of Peri-Condensed Pyrroles. Synthesis of 4H-Naphthocarbazole. A New Route to Nitrotriphenylenes
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Reaction of 1-nitrotriphenylene (7a) with triethylphosphite (Cadogan reaction) produces 4H-naphthocarbazole, a likely component of fossil fuels.Surprisingly 7a and its 2-isomer are obtained from treatment of triphenylene with sulfuric acid/trifluoroacetic anhydride in nitromethane.Correlation between ultraviolet spectra and substitution reactions in peri-condensed pyrroles and thiophenes is presented.
- Klemm, L. H.,Hall, Eliot,Sur, Sandip K.
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p. 1427 - 1429
(2007/10/02)
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- Nitration of Polycyclic Aromatic Hydrocarbons by Dinitrogen Tetraoxide. II. Synthetic and Mechanistic Aspects
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Treatment of polycyclic aromatic hydrocarbons by dinitrogen tetraoxide in dichloromethane solution leads to the clean production of mononitro derivatives with high positional selectivity in almost quantitative yields.For substrates less reactive than chrysene the addition of catalytic amounts of acid is required for the reaction to proceed at convenient rates.Being very easily performed, the method should be regarded as the best yet found for the synthesis of small amount of these, in many cases, mutagenic mononitro compounds.From studies on relative reactivities, isomer distributions, and the effect of acid, base and nitrosonium ion on the reaction, a mechanism involving initial attack of a novel electrophile, nitrosated dinitrogen tetraoxide, is proposed.The initially formed ?-complex is suggested to be transformed into the nitro ?-complex via a pathway involving radical pairs, thus explaining the observation by others of CIDNP effects on the reaction path of nitrous acid catalyzed nitration, a reaction proposed to follow the same reaction scheme.
- Eberson, Lennart,Radner, Finn
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p. 343 - 356
(2007/10/02)
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- Separation and Characterization of Mononitro Derivatives of Phenanthrene, Pyrene, Chrysene, Fluoranthene and Triphenylene
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Mononitro derivatives of selected polycyclic aromatic hydrocarbons with 3 and 4 condensed rings have been synthesized to obtain samples for measurements of mutagenic properties.Crude purification of the compounds was carried out on gravity columns prior to final purification by HPLC to a purity of approximately 99.9percent.Structural isomers were identified from NMR, MS and UV spectra.
- Svendsen, Helge,Roenningsen, Hans-Petter,Sydnes, Leiv K.,Greibrokk, Tyge
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p. 833 - 844
(2007/10/02)
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