- Methoxy substituents activated carbazole-based boron dimesityl TADF emitters
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N-Borylated emitters bearing both boron dimesityl acceptor (Mes)2B and phenoxazine or acridine donors are a class of efficient TADF emitters; however, switching to a carbazole donor nullifies the TADF characteristics. This work is targeted at i
- Chen, Deng-Gao,Chen, Meng-Chi,Chen, Wen-Cheng,Chi, Yun,Chou, Pi-Tai,Ganesan, Paramaguru,Gnanasekaran, Premkumar,Huang, Chun-Ying,Lee, Chun-Sing,Lin, Jia-An
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- Cu-Catalyzed Cross-Coupling of Nitroarenes with Aryl Boronic Acids to Construct Diarylamines
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The development and study of a simple copper-catalyzed reaction of nitroarenes with aryl boronic acids to form diarylamines that uses phenyl silane as the stoichiometric terminal reductant is described. This cross-coupling reaction requires as little as 2 mol % of CuX and 4 mol % of diphosphine for success and tolerates a broad range of functional groups on either the nitroarene or the aryl boronic acid to afford the amine in good yield. Mechanistic investigations established that the cross-coupling reaction proceeds via a nitrosoarene intermediate and that copper is required to catalyze both the deoxygenation of the nitroarene to afford the nitrosoarene and C-NAr bond formation of the nitrosoarene with the aryl boronic acid.
- Guan, Xinyu,Zhu, Haoran,Driver, Tom G.
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p. 12417 - 12422
(2021/10/12)
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- Continuous Synthesis of Aryl Amines from Phenols Utilizing Integrated Packed-Bed Flow Systems
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Aryl amines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to aryl amine synthesis using dehydrative amination of phenols with amines and styrene under continuous-flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding aryl amines, with small amounts of easily removable co-products (i.e., H2O and alkanes), in multistep continuous-flow reactors in the presence of heterogeneous Pd catalysts. The high product selectivity and functional-group tolerance of this method allowed aryl amines with diverse functional groups to be selectively obtained in high yields over a continuous operation time of one week.
- Ichitsuka, Tomohiro,Kobayashi, Shū,Koumura, Nagatoshi,Sato, Kazuhiko,Takahashi, Ikko
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p. 15891 - 15896
(2020/07/13)
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- Nickel-catalyzed N-arylation of amines with arylboronic acids under open air
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In this study, a well-defined, novel NHC-Ni complex was developed and used to catalyze the N-arylation of alkyl- and arylamines with arylboronic acids in a rare version of Chan-Lam coupling. Although the same coupling using copper catalysts has been widely studied, the nickel-catalyzed version is rare and normally requires 10–20 mol% catalyst loading. This novel NHC-Ni complex in combination with 4,4′-dimethyl-2,2′-bipyridine, however, proved to be an effective catalyst that lowered the required catalyst loading to only 2.0 mol%.
- Ando, Shin,Hirota, Yurina,Matsunaga, Hirofumi,Ishizuka, Tadao
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supporting information
p. 1277 - 1280
(2019/04/10)
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- Hole transporting material taking carbazoles bonded with tetracarbon chain as core as well as preparation method and application of hole transporting material
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The invention discloses a novel hole transporting material taking carbazoles bonded with a tetracarbon chain as a core as well as a preparation method and application of the novel hole transporting material. The hole transporting material taking carbazole
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Paragraph 0080; 0092; 0093; 0094; 0095
(2019/07/04)
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- A new kind of a hole transporting material and its preparation method and application
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The invention discloses a novel hole transport material, and a preparation method and application thereof. The structural formula of the novel hole transport material is disclosed as Formula (I), wherein R1-R28 are respectively hydrogen (H) or methoxy gro
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Paragraph 0058
(2017/09/26)
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- Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air
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To achieve efficient palladium-catalyzed cross-coupling reaction under mild reaction conditions with the flexible steric bulk strategy, a series of Pd-PEPPSI (PEPPSI: pyridine-enhanced precatalyst preparation, stabilization, and initiation) complexes C1-C6 were synthesized and characterized, in which unsymmetric flexible steric bulk was introduced on the N-aryl of ancenaphthyl skeleton. These well-defined palladium complexes were found to be excellent precatalysts for Buchwald-Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence of 0.5-0.1 mol % palladium loading. A wide range of aryl- and heteroaryl chlorides as well as various amines were compatible. The oxidative addition of aryl chlorides is revealed to be the rate-determining step in the catalytic cycle. The catalytic activity can be enhanced by introducing electron-donating groups to the Pd-PEPPSI complexes. This type of Pd-PEPPSI precatalyst showed the most efficiency reported to date for the challenging C-N cross-coupling reactions requiring no anhydrous and inert atmosphere protections, suggesting flexible steric bulk as a promising catalyst design strategy.
- Lan, Xiao-Bing,Li, Yinwu,Li, Yan-Fang,Shen, Dong-Sheng,Ke, Zhuofeng,Liu, Feng-Shou
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p. 2914 - 2925
(2017/03/23)
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- Antioxidant effects of the hydroxy groups in the simple phenolic carbazoles
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Antioxidant activities of the simple phenolic carbazoles 5-11 were evaluated by 2,2-diphenyl-1-picrylhydrazyl and 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate)+ radical scavenging assays. The simple phenolic carbazoles 5-7, 9, and 11 exhibited stronger antioxidant activities than α-tocopherol, and similar antioxidant activities as phenolic carbazole alkaloids carazostatin (1), and carbazomadurins A (3) and B (4). Bond dissociation energies and highest occupied molecule orbital energy levels of a series of phenolic carbazoles including phenolic carbazole alkaloids were calculated. The reducing ability of the phenolic carbazole core could be important role for the antioxidant activity of carbazole alkaloids 1, 3, and 4.
- Hieda, Yuhzo,Hatae, Noriyuki,Anraku, Makoto,Matsuura, Nobuyasu,Uemura, Kazuhide,Hibino, Satoshi,Choshi, Tominari,Tomida, Hisao,Hori, Osamu,Fujioka, Haruto
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p. 120 - 132
(2016/03/01)
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- HOLE-TRANSPORTING MATERIAL FOR INORGANIC/ORGANIC HYBRID PEROVSKITE SOLAR CELLS
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Provided is a hole-transporting compound having a novel structure, and more particularly, a hole-transporting compound for an inorganic/organic hybrid perovskite solar cell. An inorganic/organic hybrid perovskite-based solar cell using the hole-transporti
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- O-methoxy substituents in spiro-OMeTAD for efficient inorganic-organic hybrid perovskite solar cells
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Three spiro-OMeTAD derivatives have been synthesized and characterized by 1H/13C NMR spectroscopy and mass spectrometry. The optical and electronic properties of the derivatives were modified by changing the positions of the two methoxy substituents in each of the quadrants, as monitored by UV-vis spectroscopy and cyclic voltammetry measurements. The derivatives were employed as hole-transporting materials (HTMs), and their performances were compared for the fabrication of mesoporous TiO2/CH 3NH3PbI3/HTM/Au solar cells. Surprisingly, the cell performance was dependent on the positions of the OMe substituents. The derivative with o-OMe substituents showed highly improved performance by exhibiting a short-circuit current density of 21.2 mA/cm2, an open-circuit voltage of 1.02 V, and a fill factor of 77.6% under 1 sun illumination (100 mW/cm2), which resulted in an overall power conversion efficiency (PCE) of 16.7%, compared to ～15% for conventional p-OMe substituents. The PCE of 16.7% is the highest value reported to date for perovskite-based solar cells with spiro-OMeTAD.
- Jeon, Nam Joong,Lee, Hag Geun,Kim, Young Chan,Seo, Jangwon,Noh, Jun Hong,Lee, Jaemin,Seok, Sang Il
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supporting information
p. 7837 - 7840
(2014/06/23)
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- A recyclable Cu-catalyzed C-N coupling reaction in water and its application to synthesis of imidazo[1,2-a]quinoxaline
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Polystyrene-supported pyrrole-2-carbohydrazide (PSP) was synthesized and combined with CuI to make up a recyclable heterogeneous catalytic system for Ullmann-type C-N coupling reaction in water. In which, a variety of functionalized aryl halides animated efficiently with anilines, benzylamine, aliphatic amines, and imidazole. its preliminary application resulted in a more practical synthesis of imidazo[1,2-a]quinoxaline.
- Huang, Liye,Yu, Ruina,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 8974 - 8977
(2013/09/23)
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- Synthetic approach for constructing the 1-oxygenated carbazole core and its application to the preparation of natural alkaloids
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An efficient synthetic approach for the construction of the 1-oxygenated carbazole core is described. The condensation of cyclohexane-1,2-diones with a series of anilines yielded the corresponding 2-anilinocyclohex-2-en-1-ones, followed by the one-pot aromatization/methylation process of the latter to provide N-aryl-2-methoxyanilines. A palladium(II)-catalyzed cyclization of these N-aryl-2-methoxyanilines afforded the desired 1-methoxycarbazole frame in high overall yields. This protocol was implemented for the total synthesis of the naturally occurring glycozolicine and 6-methoxymurrayanine.
- Bautista, Rafael,Jerezano, Alberto V.,Tamariz, Joaquin
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p. 3327 - 3336,10
(2012/12/11)
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- Synthetic approach for constructing the 1-oxygenated carbazole core and its application to the preparation of natural alkaloids
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An efficient synthetic approach for the construction of the 1-oxygenated carbazole core is described. The condensation of cyclohexane-1,2-diones with a series of anilines yielded the corresponding 2-anilinocyclohex-2-en-1-ones, followed by the one-pot aromatization/methylation process of the latter to provide N-aryl-2-methoxyanilines. A palladium(II)-catalyzed cyclization of these N-aryl-2-methoxyanilines afforded the desired 1-methoxycarbazole frame in high overall yields. This protocol was implemented for the total synthesis of the naturally occurring glycozolicine and 6-methoxymurrayanine. Georg Thieme Verlag Stuttgart · New York.
- Bautista, Rafael,Jerezano, Alberto V.,Tamariz, Joaquín
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p. 3327 - 3336
(2013/01/15)
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- Synthesis of oxygenated carbazoles by palladium-mediated oxidative double C-H activation of diarylamines assisted by microwave irradiation
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Microwave irradiation in the presence of palladium acetate and traces of dimethylformamide allows the fast and efficient cyclodehydrogenation of diphenylamines into carbazoles. The scope of the microwave-assisted reaction is broader than that of the one using conventional conditions in that it allows the preparation of oxygenated carbazoles without apparent loss in yield. The applicability of the method to the preparation of carbazole alkaloids has been demonstrated by the development of a total synthesis of murrayafoline A, which proceeds in 50% overall yield from commercially available materials and is the shortest and most efficient route for the preparation of this alkaloid to date. Georg Thieme Verlag Stuttgart.
- Sridharan, Vellaisamy,Martín, Ma. Antonia,Menéndez, J. Carlos
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p. 2375 - 2378
(2008/02/09)
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- An inexpensive and efficient copper catalyst for N-arylation of amines, amides and nitrogen-containing heterocycles
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An inexpensive and efficient catalyst system has been developed for the N-arylation of nitrogen-containing compounds including a variety of amines, amides, indole and imidazole. This simple protocol uses CuI as the catalyst, commercial available pipecolinic acid as the new ligand, K2CO 3 as the base and DMF as the solvent.
- Guo, Xun,Rao, Honghua,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 2197 - 2202
(2007/10/03)
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- A fully integrated high-throughput screening methodology for the discovery of new polyolefin catalysts: Discovery of a new class of high temperature single-site group (IV) copolymerization catalysts
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For the first time, new catalysts for olefin polymerization have been discovered through the application of fully integrated high-throughput primary and secondary screening techniques supported by rapid polymer characterization methods. Microscale 1-octene primary screening polymerization experiments combining arrays of ligands with reactive metal complexes M(CH2Ph)4 (M = Zr, Hf) and multiple activation conditions represent a new high-throughput technique for discovering novel group (IV) polymerization catalysts. The primary screening methods described here have been validated using a commercially relevant polyolefin catalyst, and implemented rapidly to discover the new amide-ether based hafnium catalyst [η2- (N,O)-(2-MeO-C6H4) (2,4,6-Me3C6H2)N]Hf (CH2Ph)3 (1), which is capable of polymerizing 1-octene to high conversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondary screening experiments performed on a focused 96-member amine-ether library demonstrated the versatile high temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significant performance improvements over the initial primary screening discovery. Conventional one gallon batch reactor copolymerizations performed using selected amide-ether hafnium compounds confirmed the performance features of this new catalyst class, serving to fully validate the experimental results from the high-throughput approaches described herein.
- Boussie, Thomas R.,Diamond, Gary M.,Goh, Christopher,Hall, Keith A.,LaPointe, Anne M.,Leclerc, Margarete,Lund, Cheryl,Murphy, Vince,Shoemaker, James A. W.,Tracht, Ursula,Turner, Howard,Zhang, Jessica,Uno, Tetsuo,Rosen, Robert K.,Stevens, James C.
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p. 4306 - 4317
(2007/10/03)
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- A new reaction of cyclohexanone enolate with nitroarenes
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Reaction of cyclohexanone enolate with some nitroarenes carried out at 60-80°C proceeds via addition to the nitro group followed by a series of transformations giving o-hydroxydiarylamines.
- Moskalev,Makosza
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p. 1248 - 1249
(2007/10/03)
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- Aryllead Triacetates: Regioselective Reagents for N-Arylation of Amines
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Aryllead triacetates have been found to be regioselective reagents for the mono N-arylation of a range of aromatic, heterocyclic and aliphatic amines under mild and neutral conditions in a reaction catalysed by copper diacetate.The arylation of arylamines was unaffected by the steric hindrance of the arylamine but was dependent on the arylamine basicity.In addition, the position of oxidisable substituents on both the aryllead triacetate and the arylamine was found to be important due to a competing oxidation-reduction reaction.The arylation of heterocyclic amines proceeded in modest to good yields whilst aliphatic amines were arylated in poor to modest yields.The mechanism proposed for these reactions involves transfer of the aryl group onto copper forming a copper(III) intermediate which subsequently undergoes ligand coupling to give the N-arylated amine and the catalytic CuI species.
- Barton, Derek H. R.,Donnelly, Dervilla, M. X.,Finet, Jean-Pierre,Guiry, Patrick J.
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p. 2095 - 2102
(2007/10/02)
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