- Synthesis of Triply Fused Porphyrin-Nanographene Conjugates
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Two unprecedented porphyrin fused nanographene molecules, 1 and 2, have been synthesized by the Scholl reaction from tailor-made precursors based on benzo[m]tetraphene-substituted porphyrins. The chemical structures were validated by a combination of high
- Chen, Qiang,Brambilla, Luigi,Daukiya, Lakshya,Mali, Kunal S.,De Feyter, Steven,Tommasini, Matteo,Müllen, Klaus,Narita, Akimitsu
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- Non-palindromic (C^C^D) gold(iii) pincer complexes are not accessible by intramolecular oxidative addition of biphenylenes - an experimental and quantum chemical study
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We herein report on the synthesis of biphenylenes substituted with a pyridine (N), a phosphine (P) and a carbene (C′) donor as well as a carbene donor with additional pyridine in the lateral position. We describe the synthesis and structures of derived gold(i) complexes, which we tried to use for the synthesis of non-palindromic [(C^C^D)AuIII] pincer complexes by means of an intramolecular oxidative addition of the strained biphenylene ring. However, the anticipated formation of gold(iii) complexes failed due to kinetic and thermodynamic reasons, which we extensively investigated by quantum chemical calculations. Furthermore, we shed light on the oxidative addition of biphenylene to two different gold(i) systems reported in the literature. Our comprehensive quantum-chemical analysis is complemented by NMR experiments.
- Breher, Frank,Feuerstein, Wolfram
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- Synthesis and Physical Properties of Strained Doubly Phosphorus-Bridged Biaryls and Viologens
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New P/N-containing π-electron systems comprising fully planar biaryl arrays are synthesized by multiple radical phosphanylation. The biaryl moiety in these highly strained planar π-systems is rigidified by double P-bridging. The electronic properties of the core biaryl entity are varied by introducing N-donor substituents or by installing N-atoms within the π-system, thereby moving to the viologen core structure. The electrochemical and photophysical properties of these compounds are discussed and compared with those of related systems.
- Greulich, Tobias W.,Yamaguchi, Eriko,Doerenkamp, Carsten,Lübbesmeyer, Maximilian,Daniliuc, Constantin G.,Fukazawa, Aiko,Eckert, Hellmut,Yamaguchi, Shigehiro,Studer, Armido
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Read Online
- 2,2′,6-Tribromobiphenyl via transition-metal-free ARYNE coupling: A valuable tool in the synthesis of biphenyls
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We report a high yielding synthesis of 2,2′,6-tribromobiphenyl (TBBP) via aryne coupling, and we discuss the fundamental influence of the reaction conditions. Georg Thieme Verlag Stuttgart - New York.
- Bonnafoux, Laurence,Colobert, Fran?oise,Leroux, Frédéric R.
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Read Online
- The "Aryne" route to biaryls featuring uncommon substituent patterns
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1,2-Didehydroarenes ("arynes") mediate as extremely reactive, short-lived intermediates in selective aryl-aryl coupling processes to form biaryls with unprecedented substituent patterns (see scheme, X = H, F, Cl). Possible applications include the synthesis of novel ligands for asymmetric catalysis.
- Leroux, Frederic,Schlosser, Manfred
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Read Online
- Excitation-adjustable single-component organic triarylboron room-temperature phosphorescent material
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The invention belongs to the field of organic room temperature luminescent materials, and discloses a single-component organic triarylboron room-temperature phosphorescent material with adjustable excitation and a molecular structure thereof. Use of benze
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Paragraph 0044; 0049-0052
(2021/10/16)
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- Synthetic method for optically pure double-helix oligomeric tetra-benzocyclooctene substances
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The invention discloses a synthetic method for optically pure double-helix oligomeric tetra-benzocyclooctene substances. The synthetic method comprises the following steps: (1) carrying out oxidative cross-coupling on diiodo dimethoxy biphenyl (51) and 2,2',6,6'-biphenyl tetrabromide (97) to obtain 1,16-dibromo-8,9-dimethoxy tetra-benzocyclooctene (96); (2) splitting the compound (96), thus obtaining optically pure (S, S)-96 and (R, R)-96; (3) taking the compound (96) as a raw material, synthesizing an intermediate (116) containing 6 benzene rings; (4) splitting the intermediate (116) to obtain (M)-116 and (P)-116; (5) making the optically pure (S, S)-96 and (M)-116 reacted to obtain target products, namely (M) -117, (M)-149 and (M)-150; and/or: making the (R, R)-96 and (P)-116 reacted to obtain target products, namely (P)-117, (P)-149 and (P)-150.
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Paragraph 0045; 0046
(2017/07/31)
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- Adding Four Extra K-Regions to Hexa-peri-hexabenzocoronene
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A multistep synthesis of hexa-peri-hexabenzocoronene (HBC) with four additional K-regions was developed through a precursor based on two benzotetraphene units bridged with p-phenylene, featuring preinstalled zigzag moieties. Characterization by laser deso
- Dumslaff, Tim,Yang, Bo,Maghsoumi, Ali,Velpula, Gangamallaiah,Mali, Kunal S.,Castiglioni, Chiara,De Feyter, Steven,Tommasini, Matteo,Narita, Akimitsu,Feng, Xinliang,Müllen, Klaus
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supporting information
p. 4726 - 4729
(2016/05/09)
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- GRAPHENE NANORIBBONS WITH CONTROLLED ZIG-ZAG EDGE AND COVE EDGE CONFIGURATION
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Provided are graphene nanoribbons with controlled zig-zag edge and cove edge configuration and methods for preparing such graphene nanoribbons. The nanoribbons are selected from the following formulae.
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Page/Page column 39; 42
(2015/09/22)
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- A simple primary amine catalyst for enantioselective α-hydroxylations and α-fluorinations of branched aldehydes
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A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mechanism for α-functionalizations. Promising initial results in α-amination and α-chlorination reactions support this hypothesis.
- Witten, Michael R.,Jacobsen, Eric N.
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supporting information
p. 2772 - 2775
(2015/06/16)
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- COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE INCLUDING THE SAME
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This invention relates to a compound for an organic electroluminescent device and to an organic electroluminescent device including the same. This compound for an organic electroluminescent device including the same is improved in thermal stability and light emission efficiency. When this compound is used as a hole transport layer material, a triplet energy of a phosphorescent light emitting material is increased, thus improving the efficiency of the organic electroluminescent device.
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- Asymmetric sonogashira coupling with a chiral palladium imidazoindole phosphine complex
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The asymmetric Sonogashira coupling of 1-(2,6-di?-bromophenyl) naphthalene or 4,16-dibromo[2,2]paracyclophane with various terminal alkynes was carried out with a palladium complex of a homochiral imidazoindole phosphine, a derivative of a (3R,9aS)-2-aryl-[3-(2-dialkylphosphanyl)phenyl]tetrahydro-1H- imidazo[1,5a]indol-1-one, to give the corresponding axially chiral monoalkynylated biaryl products with up to 72% enantiomeric ?-excess. Georg Thieme Verlag Stuttgart · New York.
- Zhou, Haifeng,Uozumi, Yasuhiro
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supporting information
p. 2550 - 2554
(2013/12/04)
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- Transition-metal-free atropo-selective synthesis of biaryl compounds based on arynes
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A modular way towards biaryls: Highly enantioenriched biphenyls can be prepared based on a transition-metal-free aryl-aryl coupling followed by efficient desymmetrization or deracemization and chemoselective functionalization (see scheme). Copyright
- Leroux, Frédéric R.,Berthelot, Ana?s,Bonnafoux, Laurence,Panossian, Armen,Colobert, Fran?oise
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supporting information
p. 14232 - 14236
(2013/01/15)
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- Ladder oligo(m -aniline)s: Derivatives of azaacenes with cross-conjugated π-systems
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We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-member
- Rajca, Andrzej,Boratynski, Przemyslaw J.,Olankitwanit, Arnon,Shiraishi, Kouichi,Pink, Maren,Rajca, Suchada
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supporting information; body text
p. 2107 - 2120
(2012/05/20)
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- PROCESS FOR THE SYNTHESIS OF 2,2',6-TRIBROMOBIPHENYL
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A process for the synthesis of 2,2′,6-tribromobiphenyl.
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Page/Page column 2
(2010/06/16)
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- Drastic change in racemization barrier upon redox reactions: Novel chiral-memory units based on dynamic redox systems
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The helical configuration of dication dyes 22+ with a dihydrodibenzoxepin unit remained unchanged even at high temperature, whereas the corresponding neutral electron donors 1 with a tetrahydrophenanthroxepin skeleton easily underwent racemization. Due to their electrochemical bistability, electron exchange between 1 and 22+ is prohibited. Thus, the above electrochromic pairs can serve as novel chiral-memory units where redox reactions trigger switching between an "erasable/writable"-state (1) and a "memorizing"-state (22+).
- Suzuki, Takanori,Wada, Kazuhisa,Ishigaki, Yusuke,Yoshimoto, Yasuyo,Ohta, Eisuke,Kawai, Hidetoshi,Fujiwara, Kenshu
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supporting information; scheme or table
p. 4100 - 4102
(2010/09/06)
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- LIVING RADICAL POLYMERIZATION PROMOTER
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An organobismuth compound represented by the formula (1) and a method for preparing a living radical polymer using the organobismuth compound. In the formula (1), R1 to R3 each represent a C1-C8 alkyl group, an aryl group, a substituted aryl group, an aromatic heterocyclic group or a group represented by the formula (2) where at least one of R1 to R3 is a group represented by the formula (2), wherein R4 and R5 each represent a C3-C8 alkyl group, an aryl group or a substituted aryl group, and R6 to R8 each represent a hydrogen atom, a C1-C8 alkyl group, an aryl group or a substituted aryl group.
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Page/Page column 14
(2009/12/27)
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- Chiral bromine-lithium exchange catalyzed by diamines
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Different classes of prochiral polyhalide compounds have been tested in a chiral bromine-lithium exchange in the presence of different diamines with enantiomeric excesses of up to 63%.
- Perron, Quentin,Praz, Jezabel,Alexakis, Alexandre
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scheme or table
p. 1004 - 1007
(2009/10/23)
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- Ring opening of aziridines with ortho-bromophenyl metal reagents: synthesis of 2-substituted indolines
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Stabilized ortho-bromo phenyllithium reagents, generated via lithium-halogen exchange of aryl iodides, undergo regioselective ring opening of mono-substituted N-Boc, N-Cbz, and N-tosyl-protected aziridines in good to excellent yields. The resulting ortho-
- Michaelis, David J.,Dineen, Thomas A.
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body text
p. 1920 - 1923
(2009/08/17)
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- Synthesis and spectroscopic study of silacyclyne-substituted phenyleneethynylenes
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A series of 1,1-dimethyl-4,5:8,9-dibenzo-1-silacycloundeca-4,8-diene-2,6,10-triyne (DST)-substituted phenyleneethynylenes were successfully synthesized by reaction of Me2SiCl2 with dimagnesium dianions which had been prepared from 2,
- Mao, Guoliang,Orita, Akihiro,Matsuo, Daisuke,Hirate, Takayoshi,Iwanaga, Tetsuo,Toyota, Shinji,Otera, Junzo
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supporting information; experimental part
p. 2860 - 2864
(2009/09/06)
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- Process for the synthesis of 2,2 ,6-tribromobiphenyl
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A process for the synthesis of 2,2',6-tribromobiphenyl
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(2008/06/13)
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- PROCESS FOR THE SYNTHESIS OF 2,2',6-TRIBROMOBIPHENYL
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A process for the synthesis of 2,2',6-tribromobiphenyl.
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Page/Page column 4
(2008/06/13)
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- Palladium-catalyzed aryl amination-heck cyclization cascade: A one-flask approach to 3-substituted indoles
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(Chemical Equation Presented) Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation of a single indole regioisomer, which can be functionalized in situ by N-arylation (see scheme). dba = dibenzylideneacetone, dppf = 1,1′-bis(diphenylphospanyl)ferrocene.
- Jensen, Thomas,Pedersen, Henrik,Bang-Andersen, Benny,Madsen, Robert,Jorgensen, Morten
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p. 888 - 890
(2008/09/20)
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- A practical transition metal-free aryl-aryl coupling method: Arynes as key intermediates
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Upon treatment of various aryllithium intermediates with 1,2-dibromobenzene or 1-bromo-2-iodobenzene, dissymmetrical ortho,ortho′-di-, tri-and even tetrasubstituted bromo- or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β-elimination of a lithium halide and, stabilization of the resulting 2-biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal-free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono- and diphosphine ligands.
- Leroux, Frederic R.,Bonnafoux, Laurence,Heiss, Christophe,Colobert, Francoise,Lanfranchi, Don Antoine
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p. 2705 - 2713
(2008/09/19)
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- PROCESS FOR THE PREPARATION OF ASYMMETRICALLY SUBSTITUTED BIARYLDIPHOSPHINES
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Provided is a process for the preparation of asymmetrically substituted biaryldiphosphine ligands of the formula, (I) wherein R1 is C1-6-alkyl or C3-10-cycloalkyl optionally substituted with one or more halogen atoms, and R2 and R3 are equal and are C5-10-cycloalkyl or C1-6-alkyl, or R2 is C5-10-cycloalkyl or C1-6-alkyl, and R3 is aryl optionally substituted with one or more substituents selected from the group consisting of halogen atoms, nitro, amino, C1-6-alkyl, C1-6-alkoxy and di-C1-6-alkylamino groups, and each C1-6-alkyl, C1-6-alkoxy, di-C1-6-alkylamino and C5-10-cycloalkyl group in R2 and R3 optionally being substituted with one or more halogen atoms, from 2,2’, 6, 6’-tetra-bromobiphenyl by a sequence of bromine-metal exchanges and subsequent reactions.
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Page/Page column 14-15
(2008/06/13)
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- PROCESS FOR THE PREPARATION OF ASYMMETRICALLY SUBSTITUTED BIARYLDIPHOSPHINES
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Provided is a process for the preparation of asymmetrically substituted biaryldiphosphine ligands of the formula (I), wherein R1 is C1-6-alkyl or C3-10-cycloalkyl optionally substituted with one or more halogen atoms, and R2 and R3 are equal and are selected from the group consisting of aryl, C5-10-cycloalkyl and C1-6-alkyl, or R2 is C5-10-cycloalkyl or C1-6-alkyl, and R3 is aryl optionally substituted with one or more substituents selected from the group consisting of halogen atoms, nitro, amino, C1-6-alkyl, C1-6-alkoxy and di-C1-6-alkylamino groups, and each C1-6-alkyl, C5-10-cycloalkyl, C1-6-alkoxy and di-C1-6-alkylamino group in R2 and R3 optionally being substituted with one or more halogen atoms, from 2,2’,6,6’-tetrabromobiphenyl by a sequence of brominemetal exchanges and subsequent reactions.
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Page/Page column 16
(2010/02/15)
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- Process for the preparation of asymmetrically substituted biaryldiphosphines
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Provided is a process for the preparation of asymmetrically substituted biaryldiphosphine ligands of the formula wherein R1 is C1-6-alkyl or C3-10-cycloalkyl optionally being substituted with one or more halogen atoms, and R2 and R3 are independently selected from the group consisting of aryl, C5-10-cycloalkyl and C1-6-alkyl, wherein each aryl moiety is optionally substituted with one or more substituents selected from the group consisting of halogen atoms, nitro, amino, C1-6-alkyl, C1-6-alkoxy and di-C1-6-alkylamino groups, and each C1-6-alkyl, C1-6-alkoxy, di-C1-6-alkylamino and C5-10-cycloalkyl group in R2 and R3 optionally being substituted with one or more halogen atoms, from 2,2',6,6'-tetrabromobiphenyl by a sequence of halogen-metal exchanges and subsequent reactions.
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Page/Page column 11
(2010/02/15)
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- Formation of 3-halobenzyne: Solvent effects and cycloaddition adducts
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Noncoordinating solvents permit the halogen-metal exchange-induced formation of benzyne (aryne) from di- and trihalobenzene precursors in the presence of cyclopentadiene to give 1,4-dihydro-1,4-methano-naphthalenes. Studies with mixed halide precursors and nonacidic Diels-Alder diene traps reveal that ethereal and hydrocarbon solvents influence the halide leaving group facility, resulting in a reversal of 3-halobenzyne regioselectivity.
- Coe, Jotham W.,Wirtz, Michael C.,Bashore, Crystal G.,Candler, John
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p. 1589 - 1592
(2007/10/03)
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- 1-Aryl-3,3-dialkyltriazenes: A convenient synthesis from dry arenediazonium o-benzenedisulfonimides - A high yield break down to the starting dry salts and efficient conversions to aryl iodides, bromides and chlorides
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This research comprises three parts. The first part regards the synthesis of 1-aryl-3,3-dialkyltriazenes 3 by reaction of dry arenediazonium o-benzenedisulfonimides 1, also coming from weakly basic aromatic amines with dimethylamine or diethylamine in aqueous solution at 0-5 °C. Yields were usually greater than 90% and there was the possibility of recovering the o-benzenedisulfonimide (5), which could be reused to prepare the salts 1. In the second part it was demonstrated that there is the possibility of reconverting the triazenes 3 into the starting stable dry salts 1 by using 5 as acid. The reactions were carried out in glacial acetic acid at 50-55 °C and normally afforded salts 1 in yields of around 90-99%. The third part concerns the setting up of two procedures for the conversion of 3 to aryl iodides 9, bromides 10 and chlorides 11. Procedure A used the corresponding aqueous hydrogen halides in acetonitrile at r.t. or 60 °C, sometimes in the presence of aqueous HBF4, sometimes Cu powder (25 examples, yields 65%-88%). Procedure B usually used anhydrous methanesulfonic acid and tetraalkylammonium halides in anhydrous acetonitrile at temperatures varying from r.t. to 80 °C, sometimes in the presence of Cu (16 examples, yields 65-88%).
- Barbero,Degani,Diulgheroff,Dughera,Fochi
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p. 2180 - 2190
(2007/10/03)
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- A One-Pot Synthesis of m-Terphenyls via a Two-Aryne Sequence
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Aryl-Grignards (3+ equiv) react with 2,6-dibromoiodobenzene or other 1,2,3-trihalobenzenes to give 2,6-diarylphenylmagnesium halides.The mechanism involves Grignard exchange at the central halogen, followed by two cycles of magnesium halide loss and regioselective capture of the resulting aryne by the aryl-Grignard reagent (Scheme I).Typical examples are shown in Table I.The method is especially applicable to m-terphenyls in which the "outer" rings are identical and/or in which substitution at the 2' or other positions of the "central" ring is desired.
- Du, Chi-Jen Frank,Hart, Harold,Ng, Kwok-Keung Daniel
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p. 3162 - 3165
(2007/10/02)
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