- An efficient synthesis of triphenylene
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Triphenylene (1) has been obtained in 66% yield by decomposition of 1-fluoro-2-sodiobenzene. The corresponding ortho-lithio, potassio and caesio compounds gave mainly other, unidentified products.
- Fossatelli,Brandsma
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- Gold-catalyzed cyclotrimerization of arynes for the synthesis of triphenylenes
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A novel and efficient Au(I)-catalyzed cyclotrimerization of arynes, generated by fluoride-induced elimination of Kobayashi's silylaryl triflates, is described. The reactions led to the formation of triphenylenes in 45-88% yields under mild conditions.
- Chen, Lili,Zhang, Changyuan,Wen, Chunxiao,Zhang, Kun,Liu, Wenfeng,Chen, Qian
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- Trialkylsilylethynyl-substituted triphenylenes and hexabenzocoronenes: Highly soluble liquid crystalline materials and their hole transport abilities
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Four triphenylene (TP) and four hexa-peri-hexabenzocoronene (HBC) derivatives with trialkylsilylethynyl groups were prepared and characterized by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction measurements. All compounds were highly soluble in less-polar organic solvents and exhibited a columnar phase, Colh or Colr for the TPs, and Colh for the HBCs. The hole transport ability in the HBCs' columnar phase, 0.4-1.5×10-3 cm2 V-1 s-1 at 40-180°C, and its temperature dependence were determined by the time-of-flight method using a solution technique.
- Hirose, Takuji,Miyazaki, Yutaro,Watabe, Mizuki,Akimoto, Sho,Tachikawa, Tatsuya,Kodama, Koichi,Yasutake, Mikio
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- Synthesis of Tribenzo[ b, d, f]azepines via Cascade π-Extended Decarboxylative Annulation Involving Cyclic Diaryliodonium Salts
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Various functionalized tribenzo[b,d,f]azepines were prepared efficiently with the readily available 2-aminobenzoic acids and cyclic hypervalent diaryliodonium reagents as starting materials under Pd(II) catalysis. The key of this step-economical protocol is that the carboxylic acid functionality was employed as both a traceless directing group for the N-H activation/arylation and a functional handle for the tandem π-extended decarboxylative annulation.
- Hu, Tao,Ye, Zenghui,Zhu, Kai,Xu, Kai,Wu, Yanqi,Zhang, Fengzhi
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- Aromatic Metamorphosis of Indoles into 1,2-Benzazaborins
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Among the plethora of aromatic compounds, indoles represent a privileged class of substructures that is ubiquitous in natural products and pharmaceuticals. While numerous exocyclic functionalizations of indoles have provided access to a variety of useful derivatives, endocyclic transformations involving the cleavage of the C2-N bond remain challenging due to the high aromaticity and strength of this bond in indoles. Herein, we report the "aromatic metamorphosis" of indoles into 1,2-benzazaborins via the insertion of boron into the C2-N bond. This endocyclic insertion consists of a reductive ring-opening using lithium metal and a subsequent trapping of the resulting dianionic species with organoboronic esters. Considering that 1,2-azaborins have attracted increasing academic and industrial attention as BN isosteres of benzene, the counterintuitive aromatic metamorphosis presented herein can feasibly be expected to substantially advance the promising chemistry of 1,2-azaborins.
- Tsuchiya, Shun,Saito, Hayate,Nogi, Keisuke,Yorimitsu, Hideki
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- Pd-Catalyzed three-component coupling of terminal alkynes, arynes, and vinyl cyclopropane dicarboxylate
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A palladium-catalyzed three-component coupling involving in situ generated arynes, terminal alkynes, and vinyl cyclopropane dicarboxylate has been developed. The process demonstrates the first example of aryne chemistry combined with the ring opening of vinyl cyclopropanes. This efficient method using readily available starting materials generates two new carbon-carbon bonds in one pot.
- Garve, Lennart K. B.,Werz, Daniel B.
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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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- To flip or not to flip? Assessing the inversion barrier of the tetraphenylene framework with enantiopure 2,15-dideuteriotetraphenylene and 2,7-dimethyltetraphenylene
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(Chemical Equation Presented) Two chiral tetraphenylenes, 2,15-dideuteriotetraphenylene (7) and 2,7-dimethyltetraphenylene (15) were synthesized and resolved to address the tetraphenylene inversion barrier problem. Neutron diffraction investigation of ena
- Huang, Hui,Stewart, Timothy,Gutmann, Matthias,Ohhara, Takashi,Niimura, Nobuo,Li, Yu-Xue,Wen, Jian-Feng,Bau, Robert,Wong, Henry N. C.
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- Uncatalyzed zirconium-mediated biphenylation of o-dihalobenzenes to form triphenylenes
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The reaction of [Zr(biphe)3][(Li·(THF)4)2], where biphe is 2,2′-biphenyldiyl, with an o-dihaloarene produces a triphenylene. Two new bonds are created in this rare example of an uncatalyzed, Zr-mediated aryl-aryl bond formation. Multiple biphe fragments can be incorporated to give larger triphenylene-containing polycyclic aromatic hydrocarbons. This reaction can introduce significant strain and was demonstrated to tolerate alkyl and methoxy substituents. Copyright
- Hilton, Cameron L.,Jamison, Christopher R.,King, Benjamin T.
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- Palladium-Catalyzed Regioselective Domino Spirocyclization of Carbamoyl Chlorides with Alkynes and Benzynes
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A palladium-catalyzed domino spiro-cyclization of carbamoyl chlorides with alkynes and benzynes, involving intramolecular C?H activation to afford valuable oxindole scaffolds bearing spiro quaternary stereocenters, has been developed. This one-step synthesis of spirooxindole is both step- and atom-economic, proceeding with high regioselectivity in moderate to excellent yields. (Figure presented.).
- Wang, Chenchen,Zhao, Wenyu,Wu, Xianqing,Qu, Jingping,Chen, Yifeng
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- Catalytic Dehydrogenative Cyclization of o-Teraryls under pH-Neutral and Oxidant-Free Conditions
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A cobaloxime-catalyzed acceptorless dehydrogenative cyclization of o-teraryls was developed. In stark contrast to the established methods such as the Scholl or Mallory reactions, this method does not require any strong acids or oxidants, and shows high atom economy and a broad substrate scope. It operates at near room temperature with light as the source of energy. Acid- or oxidant-sensitive functional groups, such as 4-methoxyphenyl, unprotected benzyl alcohol, silyl ether, and thiophene groups are tolerated. Remarkably, aryls with electron-withdrawing groups, and electron-poor heteroarenes, such as pyridine and pyrimidine, can also react. Preliminary mechanistic study reveals that hydrogen gas is released during the reaction, and both light and the cobalt catalyst are important for the dehydrogenation step.
- Dong, Guangbin,Tsukamoto, Tatsuhiro
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- Synthesis of terpyridine-containing Pd(II) complexes and evaluation of their catalytic activity
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Herein, we prepare two terpyridine-containing Pd(II) complexes, [PdClL1]?solvent (A1) and [PdClL2]?2H2O (A2) (L1 = 4’-(4-carboxyl-phenyl)-2,2’:6′,2″-terpyridine, L2 = 2,6-bis(2-pyrazinyl)-4-(4-carboxyl-phenyl)pyridine), from 4’-(4-cyanophenyl)-2,2’:6′,2″-terpyridine(L1a)/2,6-bis(2-pyrazinyl)-4-(4-cyanophenyl)pyridine (L2a) and Pd(II) acetate and characterise them by several instrumental techniques. A1 and A2 are shown to be good catalysts for the coupling of 2-iodobiphenyl with iodobenzenes to afford triphenylenes, which is known to involve dual C–H bond activation and double C–C bond formation. The obtained data suggest that the mechanism of A1-and A2-mediated coupling may be similar to the reference Pd catalysts, A1 and A2 are also suitable catalysts for this cyclization process. Study on this kind of complexes is of importance to the development of novel Pd-based catalysts and triphenylene synthesis techniques.
- Yin, Sanmao,Wang, Xiaomin,Jiang, Jun,Xiao, Hongping,Li, Xinhua
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- Isolation and structures of some selenium and tellurium derivatives of 1, 4, 5, 8, 9, 12-hexabromododecahydrotriphenylene as co-crystals of triphenylene
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The synthesis and characterization of low-valent organoselenium and tellurium derivatives of hexabromododecahydrotriphenylene has been attempted. The reaction of hexabromododecahydrotriphenylene with in situ generated disodium dichalcogenides (Na2E2; E = Se, Te) afforded insoluble chalcododecahydrotriphenylene derivatives, 20, 21 respectively. Attempted aromatization of 20 and 21 using DDQ (2, 3-dichloro-5, 6-dicyano-1,4-benzoquinone) as an oxidizing agent afforded the co-crystals. The hexaselenophenyl derivative, 22 and the hexaselenocyanate derivative 23 were synthesized by the reaction of in situ generated sodium arylselenolate/potassium selenocyanate with hexabromododecahydrotriphenylene, respectively. The compounds were characterized by common spectroscopic tools and a few by single crystal x-ray crystallographic studies.
- Prasad, Poonam Rajesh,Singh, Harkesh B,Butcher, Ray J
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- Preparation of substituted triphenylenesvianickel-mediated Yamamoto coupling
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Substituted triphenylenes show promise as organic semiconductors because of their ability to form columnar liquid crystalline phases featuring extended π-stacked arrays. While there are several methods for preparing triphenylenes, including oxidative cyclization reactions such as the Scholl reaction, as well as transition metal-catalyzed aryne cyclotrimerization, these methods are not effective for electron deficient triphenylenes. Here we demonstrate that the nickel-mediated Yamamoto coupling ofo-dibromoarenes is a concise and efficient way to prepare substituted triphenylenes, including electron-deficient systems that are otherwise challenging to prepare. We also demonstrate the application of this approach to prepare electron deficient discotic mesogens composed of triphenylenes bearing imide and thioimide groups.
- LeDrew, Joshua,Maly, Kenneth E.,Schroeder, Zachary W.,Selmani, Vanessa M.
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p. 39564 - 39569
(2021/12/24)
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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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- A chemo- And regioselective Pd(0)-catalyzed three-component spiroannulation
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A chemo- and regioselective Pd(0)-catalyzed spiroannulation has been successfully developed. The key feature of this method is the use of readily available 1,2-dihaloarenes, alkynes and 2-naphthols for the rapid assembly of spirocarbocyclic molecules. Mechanistic studies revealed that this domino reaction proceeded through a cascade of oxidative addition to Pd(0), alkyne migratory insertion, and 2-naphthol-facilitated dearomatizing [4+1] spiroannulation.
- Wu, Jiaoyu,Bai, Lu,Han, Lingbo,Liu, Jingjing,Luan, Xinjun
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supporting information
p. 1117 - 1120
(2021/02/06)
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- Nickel-Catalyzed Homocoupling of Aryl Ethers with Magnesium Anthracene Reductant
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Nickel-catalyzed reductive homocoupling of aryl ethers has been achieved with Mg(anthracene)(thf) 3as a readily available low-cost reductant. DFT calculations provided a rationale for the specific efficiency of the diorganomagnesium-type two-electron reducing agent. The calculations show that the dianionic anthracene-9,10-diyl ligand reduces the two aryl ether substrates, resulting in the homocoupling reaction through supply of electrons to the Ni-Mg bimetallic system to form organomagnesium nickel(0)-ate complexes, which cause two sequential C-O bond cleavage reactions. The calculations also showed cooperative actions of Lewis acidic magnesium atoms and electron-rich nickel atoms in the C-O cleavage reactions.
- Rawat, Vishal Kumar,Higashida, Kosuke,Sawamura, Masaya
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supporting information
p. 3397 - 3403
(2021/06/28)
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- Palladium-Catalyzed Sequential Vinyl C–H Activation/Dual Decarboxylation: Regioselective Synthesis of Phenanthrenes and Cyclohepta[1,2,3-de]naphthalenes
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The application of a C(vinyl), C(aryl)-palladacycle from vinyl-containing substrates is challenging due to the interference of a reactive double bond in palladium catalysis. This Letter describes a [4 + 2] or [4 + 3] cyclization based on a C(vinyl), C(aryl)-palladacycle by employing α-oxocarboxylic acids as the insertion units under a palladium/air system. The reaction proceeded through the key vinyl C–H activation and dual decarboxylation sequence, forming phenanthrenes and cyclohepta[1,2,3-de]naphthalenes regioselectively in good yields. The synthetic versatility of this protocol is highlighted by the gram-scale synthesis and synthesizing functional material molecule.
- Jiang, Guomin,Ye, Hao,Shi, Lei,Dai, Hong,Wu, Xin-Xing
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p. 9398 - 9402
(2021/12/09)
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- Synthesis of Polybenzoacenes: Annulative Dimerization of Phenylene Triflate by Twofold C?H Activation
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Polycyclic aromatic hydrocarbons (PAHs) represent an emerging class of π-conjugated molecules in the area of optoelectronic devices and materials. Unprecedented synthetic routes to various PAHs from simple phenol derivatives by a palladium-catalyzed annulative dimerization of phenylene triflate through twofold inter- and intramolecular C?H activation have been established. The initially formed partially fused PAHs can be smoothly transformed into a variety of fully fused PAHs by the Scholl reaction. Furthermore, the reactions of phenanthrene-substituted aryl triflates proceeded regioselectively. The findings inspired the development of a rapid and efficient synthesis of polybenzoacene derivatives. This study not only allows transformation of phenyl triflates, but also discloses a new retrosynthetic strategy towards PAHs, especially polybenzoacenes.
- Uryu, Mizuho,Hiraga, Taito,Koga, Yoshito,Saito, Yutaro,Murakami, Kei,Itami, Kenichiro
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supporting information
p. 6551 - 6554
(2020/04/10)
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- Synthesis method of triphenylene compound
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The invention provides a synthesis method of a triphenylene compound. By taking 2-(trimethylsilyl)phenyl trifluoromethane sulfonate as a benzyne precursor, cesium fluoride as an alkali and 18-crown-6-ether as a phase transfer catalyst, a reaction of the precursor with 9-fluorenone oxime under the condition of no additional metal catalyst is realized through a one-pot process reaction. The reactioncondition is mild and easy to realize, the reaction overcomes the defect that transition metal or noble metal catalysts are required to be added in the previous reaction, and a brand-new way is provided for developing the triphenylene compound.
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Paragraph 0022; 0026-0037
(2020/09/30)
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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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- Phenanthrene Synthesis by Palladium(II)-Catalyzed γ-C(sp2)-H Arylation, Cyclization, and Migration Tandem Reaction
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Phenanthrene is an important structural motif in chemistry and materials science, and many synthetic routes have been developed to construct its skeleton. However, synthesis of unsymmetric phenanthrenes remains a challenge. Here, an efficient one-pot tandem reaction for the preparation of phenanthrenes via sequential γ-C(sp2)-H arylation, cationic cyclization, dehydration, and 1,2-migration was developed. A wide range of symmetric and unsymmetric phenanthrenes with diversified functional groups were synthesized with good to excellent yields.
- Gou, Bo-Bo,Yang, Hui,Sun, Huai-Ri,Chen, Jie,Wu, Junliang,Zhou, Ling
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- Aerobic and Ligand-Free Manganese-Catalyzed Homocoupling of Arenes or Aryl Halides via in Situ Formation of Aryllithiums
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Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained, and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.
- Liu, Yujia,Bergès, Julien,Zaid, Yassir,Chahdi, Fouad Ouazzani,Van Der Lee, Arie,Harakat, Dominique,Clot, Eric,Jaroschik, Florian,Taillefer, Marc
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p. 4413 - 4420
(2019/03/26)
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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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- Annulative π-Extension of Unactivated Benzene Derivatives through Nondirected C-H Arylation
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Annulative π-extension chemistry provides a concise synthetic route to polycyclic arenes. Herein, we disclose a nondirected annulation approach of unactivated simple arenes. The palladium-catalyzed 2-fold C-H arylation event facilitates tandem C-C linkage relays to furnish fully benzenoid triphenylene frameworks using cyclic diaryliodonium salts. The inseparable regioisomeric mixture of 1- and 2-methyltriphenylenes is identified by the combined analysis of ion mobility-mass spectrometry, gas-phase infrared spectroscopy, and molecular simulation studies.
- Lee, Jae Bin,Jeon, Min Ho,Seo, Jeong Kon,Von Helden, Gert,Rohde, Jan-Uwe,Zhao, Bum Suk,Seo, Jongcheol,Hong, Sung You
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supporting information
p. 7004 - 7008
(2019/09/07)
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- Gas-Phase Synthesis of Triphenylene (C18H12)
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For the last decades, the hydrogen-abstraction?acetylene-addition (HACA) mechanism has been widely invoked to rationalize the high-temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9-phenanthrenyl radical ([C14H9].) with vinylacetylene (C4H4), we present the first compelling evidence of a barrier-less pathway leading to a prototype tetracyclic PAH – triphenylene (C18H12) – via an unconventional hydrogen abstraction–vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier-less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two-dimensional, graphene-type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level.
- Zhao, Long,Xu, Bo,Ablikim, Utuq,Lu, Wenchao,Ahmed, Musahid,Evseev, Mikhail M.,Bashkirov, Eugene K.,Azyazov, Valeriy N.,Howlader, A. Hasan,Wnuk, Stanislaw F.,Mebel, Alexander M.,Kaiser, Ralf I.
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p. 791 - 797
(2019/02/19)
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- Regioselective arene homologation through rhenium-catalyzed deoxygenative aromatization of 7-oxabicyclo[2.2.1]hepta-2,5-dienes
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Combined use of oxorhenium catalysts with triphenyl phosphite as an oxygen acceptor allowed efficient deoxygenative aromatization of oxabicyclic dienes. The reaction proceeded under neutral conditions and was compatible with various functional groups. Combining this deoxygenation with regioselective bromination and trapping of the generated aryne with furan resulted in benzannulative π-extension at the periphery of the PAHs. This enabled direct use of unfunctionalized PAHs for extension of π-conjugation. Iteration of the transformations increased the number of fused-benzene rings one at a time, which has the potential to alter the properties of PAHs by fine-tuning the degree of π-conjugation, shape, and edge topology.
- Murai, Masahito,Ogita, Takuya,Takai, Kazuhiko
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p. 2332 - 2335
(2019/02/27)
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- Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way
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Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance-stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl-addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen-abstraction/acetylene-addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.
- Zhao, Long,Prendergast, Matthew B.,Kaiser, Ralf I.,Xu, Bo,Ablikim, Utuq,Ahmed, Musahid,Sun, Bing-Jian,Chen, Yue-Lin,Chang, Agnes H. H.,Mohamed, Rana K.,Fischer, Felix R.
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supporting information
p. 17442 - 17450
(2019/11/11)
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- Palladium-catalyzed cocyclotrimerization of arynes with a pyramidalized alkene
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The metal-catalyzed [2+2+2] cocycloaddition of arynes with pyramidalized alkenes is presented. The generation of a highly reactive pyramidalized alkene in the presence of a large excess of in situ-produced arynes led to the corresponding cocyclotrimerization (1:2)-adducts in good yields, establishing the first example of a palladium-based reaction of a pyramidalized alkene.
- Alonso, José M.,Quiroga, Sabela,Codony, Sandra,Turcu, Andreea L.,Barniol-Xicota, Marta,Pérez, Dolores,Guitián, Enrique,Vázquez, Santiago,Pe?a, Diego
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p. 5996 - 5999
(2018/06/18)
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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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- Palladium-Catalyzed Synthesis of Triphenylenes via Sequential C-H Activation and Decarboxylation
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A novel tandem intermolecular decarboxylative coupling reaction of o-bromobenzoic acids and aryl iodides has been developed. The method affords a range of unsymmetrically triphenylenes and displays unique regioselectivity and broad substrate scope. Mechanistically, palladium/norbornene-catalyzed C-H activation and subsequent double decarboxylative coupling reactions were involved. Moreover, the triphenylenes can also be synthesized from 2-iodobiphenyls and o-bromobenzoic acids under norbornene-free conditions.
- Yang, Yuzhong,Zhou, Bang,Zhu, Xiaoming,Deng, Guobo,Liang, Yun,Yang, Yuan
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p. 5402 - 5405
(2018/09/13)
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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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- Triphenylsulfonium topophotochemistry
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The products from the 193 nm irradiation of triphenylsulfonium nonaflate (TPS) embedded in a poly(methyl methacrylate) (PMMA) film have been characterized. The analysis of the photoproduct formation was performed using chromatographic techniques including HPLC, GPC and GC-MS as well as UV-vis and NMR spectroscopic methods. Two previously unreported TPS photoproducts, triphenylene and dibenzothiophene, were detected; additionally, GPC and DOSY-NMR spectroscopic analyses after irradiation suggested that TPS fragments had been incorporated into the polymer film. The irradiation of acetonitrile solutions containing 10% w/v PMMA and 1% w/v TPS in a 1 cm-path-length cuvette showed only a trace amount of triphenylene or dibenzothiophene, indicating that topochemical factors were important for the formation of these molecules. The accumulated evidence indicates that both products were formed by in-cage, secondary photochemical reactions: 2-(phenylthio)biphenyl to triphenylene, and diphenylsulfide to dibenzothiophene.
- Despagnet-Ayoub,Kramer,Sattler,Sattler,Labeaume,Thackeray,Cameron,Cardolaccia,Rachford,Winkler,Gray
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- Desulfurization of dibenzothiophene and dibenzothiophene sulfone via Suzuki–Miyaura type reaction: Direct access to o-terphenyls and polyphenyl derivatives
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The reactivity of dibenzothiophene (DBT) or dibenzothiophene sulfone (DBTO2) with a variety of phenylboronic acids was mediated by the nickel precursor [Ni(dippe)Cl2] in the presence of a base. The reaction was performed under relatively mild conditions (70–100 °C), in aqueous media. The study of the reactivity revealed the role of water as a hydrogen source and showed a competition between the desulfurization of the corresponding substrates via a hydrodesulfurization (HDS) or by a hydrodesulfurative cross-coupling (HDSCC) reaction. Furthermore, in the absence of water sulfur-free poly-phenylic compounds were obtained in good yields as a result of a Suzuki–Miyaura type reaction, being the main product in most of the cases the corresponding o-terphenyl derivative, these products are valuable building blocks in the synthesis of more complex materials.
- Gutiérrez-Ordaz, Rubén,García, Juventino J.
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p. 373 - 381
(2018/08/31)
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- Facile Synthesis of Polycyclic Aromatic Hydrocarbons: Br?nsted Acid Catalyzed Dehydrative Cycloaromatization of Carbonyl Compounds in 1,1,1,3,3,3-Hexafluoropropan-2-ol
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The cycloaromatization of aromatic aldehydes and ketones was readily achieved by using a Br?nsted acid catalyst in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). In the presence of a catalytic amount of trifluoromethanesulfonic acid, biaryl-2-ylacetaldehydes and 2-benzylbenzaldehydes underwent sequential intramolecular cationic cyclization and dehydration to afford phenacenes and acenes, respectively. Furthermore, biaryl-2-ylacetaldehydes bearing a cyclopentene moiety at the α-position underwent unprecedented cycloaromatization including ring expansion to afford triphenylenes. HFIP effectively promoted the cyclizations by suppressing side reactions presumably as a result of stabilization of the cationic intermediates.
- Fujita, Takeshi,Takahashi, Ikko,Hayashi, Masaki,Wang, Jingchen,Fuchibe, Kohei,Ichikawa, Junji
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p. 262 - 265
(2017/01/24)
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- Synthesis of Tribenzo[b,e,g]phosphindole Oxides via Radical Bicyclization Cascades of o-Arylalkynylanilines
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A new DTBP/Mg(NO3)2-mediated bicyclization cascade of o-arylalkynylanilines with secondary arylphosphine oxides has been developed, enabling dual C(sp2)-H functionalization along with the cleavage of the C-N bond. The combination between regioselective P-centered radical-triggered [3 + 2] cyclization and C-centered radical-induced cross-coupling in a one-pot manner delivered 27 examples of tribenzo[b,e,g]phosphindole oxides with generally high regioselectivity. A reasonable mechanism for forming such products involving radical addition-cyclization cascade is proposed.
- Li, Jie,Zhang, Wen-Wen,Wei, Xiao-Jing,Hao, Wen-Juan,Li, Guigen,Tu, Shu-Jiang,Jiang, Bo
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supporting information
p. 4512 - 4515
(2017/09/11)
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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; 0071; 0072; 0073
(2017/12/28)
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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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- A N-heterocyclic tetracarbene Pd(II) moiety containing a Pd(II)-Pb(II) bimetallic MOF for three-component cyclotrimerization via benzyne
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A novel Pd(ii)-Pb(ii) bimetallic metal-organic framework Pd(ii)-Pb(ii)-MOF (B) which contains an N-heterocyclic tetracarbene Pd(ii) moiety was synthesized based on a chelating N-heterocyclic dicarbene Pd(ii)-NHDC ligand (A) under solvothermal conditions. It can be a highly active heterogeneous catalyst for three-component cyclotrimerization via benzyne species.
- Dong, Ying,Li, Yue,Wei, Yong-Liang,Wang, Jian-Cheng,Ma, Jian-Ping,Ji, Jun,Yao, Bing-Jian,Dong, Yu-Bin
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supporting information
p. 10505 - 10508
(2016/09/02)
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- Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof
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The invention discloses an organic ligand and a Pd/Pb-based bi-metal organic framework as well as a synthetic method and application of the organic ligand and the Pd/Pb metal organic framework. A structural formula of the Pd/Pb-based bi-metal organic framework (Pd/Pb-MOF) is [Pb4(C42H28N8O8Pd)(C2O4)Br4]n, wherein n is a nonzero natural number. The Pd/Pb-based bi-metal organic framework (Pd/Pb-MOF) is used as a catalyst to be applied to catalyzing benzyne homocoupling and catalyzing three-component coupling reaction of benzyne, boracic acid and allyl halohydrocarbon. The MOF catalyst with active sites can be used for replacing some heavy metals to achieve a catalytic effect, so that the harm of the heavy metals to the environment is reduced. The MOF catalyst with the active sites is used for catalysis, so that heterocatalysis is realized; additionally, the bi-metal organic framework catalyst can be recycled for more than four times, and the catalyst is easy to recycle, so that the utilization rate of the catalyst is increased, and the cost is reduced.
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Paragraph 0068; 0073; 0074; 0075; 0076
(2016/10/08)
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- Aerobic Oxidative Intramolecular Aromatic Coupling via Heterogeneous Metal Catalysts
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An aerobic, heterogeneously catalyzed oxidative intramolecular coupling reaction of aromatic compounds is reported here. Using commercially available, recyclable heterogeneous metal catalysts, the coupling reactions of o-terphenyls and 1,ω-biarylalkanes proceeded quickly under mild conditions, i.e., at room temperature under oxygen as a co-oxidant almost all within 1 h, to provide the corresponding coupled products like triphenylenes and phenanthrenes in good to excellent yields. This reaction is an easily handled, practical, and atom-economical coupling method, which is of great importance in modern organic syntheses. (Figure presented.).
- Fujimoto, Shigenobu,Matsumoto, Kenji,Shindo, Mitsuru
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p. 3057 - 3061
(2016/10/09)
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- [N,P]-pyrrole PdCl2 complexes catalyzed the formation of dibenzo-α-pyrone and lactam analogues
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We herein report the synthesis and catalytic application of a new family of [N,P] ligands based on the pyrrole ring with alpha-phosphine or phosphole units. Their palladium complexes (3a-d) were obtained in very good yields and their catalytic properties were evaluated in the direct intramolecular arylation to obtain both benzopyranones and phenanthridinones. The air stable complex 3a exhibited the best catalytic performance of this series of complexes, using 1 mol% of catalyst in combination with microwaves to promote this reaction.
- Suárez-Meneses,Oukhrib,Gouygou,Urrutigo?ty,Daran,Cordero-Vargas,Ortega-Alfaro,López-Cortés
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p. 9621 - 9630
(2016/07/06)
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- Pd-Catalyzed Spirocyclization via C-H Activation and Benzyne Insertion
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A palladium-catalyzed spirocyclization forming spirooxindoles and spirodihydrobenzofurans has been achieved. Mechanistic studies suggest that the transformation proceeds through sequential carbopalladation, C-H activation, and benzyne insertion. Both classes of spirocycles have been synthesized in good to excellent yields, and the procedure is readily scalable.
- Yoon, Hyung,Lossouarn, Alexis,Landau, Felicitas,Lautens, Mark
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supporting information
p. 6324 - 6327
(2016/12/23)
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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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- An Approach to Tetraphenylenes via Pd-Catalyzed C-H Functionalization
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Tetraphenylenes not only are theoretically and experimentally interesting but also have potential applications in a variety of fields such as materials science, supramolecular chemistry, and asymmetric catalysis. A facile and efficient approach is reported for the syntheis of tetraphenylene and its derivatives from 2-iodobiphenyls via Pd-catalyzed C-H activation. A range of substituted tetraphenylenes can be synthesized using this method, and the reaction can be performed on gram scale with relatively high efficiency, demonstrating its practical utility. This novel approach provides easy access to tetraphenylenes and should facilitate research on the application of this type of fascinating molecules.
- Jiang, Hang,Zhang, Yu,Chen, Dushen,Zhou, Bo,Zhang, Yanghui
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supporting information
p. 2032 - 2035
(2016/06/01)
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- Regioselective synthesis of nanographenes by photochemical cyclodehydrochlorination
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Novel nanographenes were prepared by a photochemical cyclodehydrochlorination (CDHC) reaction. Chlorinated precursors were irradiated in acetone in the presence of a base or in pure benzene and underwent multiple (up to four) regioselective cyclization reactions to provide rigid π-conjugated molecules. Pure compounds were recovered in good yields by simple filtration at the end of the reaction. The CDHC reaction showed compatibility with both electron-poor and electron-rich substrates, thus allowing the synthesis of pyridine- and thiophene-fused nanographenes. It also enabled the synthesis of sterically hindered contorted π-conjugated molecules without causing full aromatization. A kinetic study showed that the CDHC reaction under the conditions used is a very fast process, and some reactions are completed within minutes. The CDHC reaction thus shows great potential as an alternative to other reactions involving harsher conditions for the preparation of nanographenes.
- Daigle, Maxime,Picard-Lafond, Audrey,Soligo, Eliane,Morin, Jean-Fran?ois
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supporting information
p. 2042 - 2047
(2016/02/18)
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- Aryne-Mediated Arylation of the 3-Benzazepine Scaffold: One-Pot Synthesis of 1-Aryl-3-methyl-2,3,4,5-tetrahydro-1 H -3-benzazepines
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The coupling of β-amino carbanions derived from 3-benzA"azeA"pines with in situ generated arynes has been demonstrated as a convenient route for the direct synthesis of a variety of 1-aryl-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepines, including the biologically active drug molecule SCH 12679.
- Singh, Kamal Nain,Singh, Paramjit,Sharma, Esha,Kaur, Manjot,Deol, Yadwinder Singh
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p. 3212 - 3220
(2015/10/19)
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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-Assisted "Aromatic Metamorphosis" of Dibenzothiophenes into Triphenylenes
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Abstract Two new palladium-catalyzed reactions of aromatic sulfur compounds enabled the conversion of dibenzothiophenes into triphenylenes in four steps. This transformation of one aromatic framework into another consists of 1) 4-chlorobutylation of the dibenzothiophene to form the corresponding sulfonium salt, 2) palladium-catalyzed arylative ring opening of the sulfonium salt with a sodium tetraarylborate, 3) an intramolecular SN2 reaction to form a teraryl sulfonium salt, and 4) palladium-catalyzed intramolecular C-S/C-H coupling through electrophilic palladation. Symmetrical as well as unsymmetrical triphenylenes of interest were synthesized in a tailor-made fashion in satisfactory overall yields. A change of heart: The invention of two palladium-catalyzed arylation reactions of organosulfur compounds enabled the transformation of dibenzothiophenes into triphenylenes and thus a fundamental change in the core aromatic structure (see scheme). Both symmetrical and unsymmetrical triphenylenes were synthesized in a tailor-made fashion in satisfactory overall yield.
- Vasu, Dhananjayan,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 7162 - 7166
(2015/06/08)
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- Mass spectrometric studies of self-condensation products of cyclohexanone under alkaline conditions and synthesis of dodecahydrotriphenylene and triphenylene from easily available reactants
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LC-MS was used to study products of cyclohexanone self-condensation under alkaline conditions. Improved methods (as compared to those described in the literature) for the preparation of dodecahydrotriphenylene and highly pure sublimed triphenylene were suggested based on the easily available and cheap reactants. Possible reasons of the low yield of the target dodecahydrotriphenylene in the step of oligomerization of cyclohexanone were identified.
- Kovalev,Kopchuk,Zyryanov,Khasanov,Rusinov,Chupakhin
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p. 1539 - 1542
(2015/03/14)
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- Use of external radical sources in flash vacuum pyrolysis to facilitate cyclodehydrogenation reactions in polycyclic aromatic hydrocarbons
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A new process to facilitate the cyclodehydrogenation of polycyclic aromatic hydrocarbons (PAHs) in flash vacuum pyrolysis (FVP) using an external radical source is described. Using hexanes as an external radical source the conversion of various PAHs to their cyclodehydrogenated products is vastly increased. Various other volatile organic compounds were also examined to determine their ability to act as external radical sources in FVP.
- Amick, Aaron W.,Martin, Sara E.
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p. 1338 - 1343
(2014/11/08)
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- Synthesis of a polymerizable benzocyclobutene that undergoes ring-opening isomerization at reduced temperature
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1-Ethoxyvinylbenzocyclobutene is a substituted benzocyclobutene that undergoes radical polymerization to produce polymers that can be crosslinked at 100-150 °C. The 4- and 5-vinyl isomers are synthesized in a 1:4 ratio via a halogenated benzyne intermediate produced from anthranilic acid, followed by cycloaddition with ethyl vinyl ether and replacement of the halogen atom with a vinyl group. Georg Thieme Verlag Stuttgart · New York.
- Pugh, Coleen,Baker, James S.,Storms, William K.
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supporting information
p. 148 - 152
(2014/01/06)
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- Use of 2-bromophenylboronic esters as benzyne precursors in the Pd-catalyzed synthesis of triphenylenes
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ortho-Substituted aryl boronates are introduced as aryne precursors for transition-metal-catalyzed transformations. On treatment with tBuOK and Pd(0), metal-bound aryne intermediates are formed that undergo effective trimerization to form useful triphenylene compounds. For meta-substituted arynes, the 3:1 product ratio in favor of non-C3 symmetric material is indicative of a benzyne mechanism.
- Garcia-Lopez, Jose-Antonio,Greaney, Michael F.
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p. 2338 - 2341
(2014/05/20)
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