- Preparation of Functionalized Diorganomagnesium Reagents in Toluene via Bromine or Iodine/Magnesium-Exchange Reactions
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A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents are prepared in toluene within 10 to 120 minutes between 78 C and 25 C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as triazene or nitro, are tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arene and alkene derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.
- Desaintjean, Alexandre,Danton, Fanny,Knochel, Paul
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supporting information
p. 4461 - 4476
(2021/08/13)
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- Copper-Free Sonogashira Coupling for High-Surface-Area Conjugated Microporous Poly(aryleneethynylene) Networks
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A modified one-pot Sonogashira cross-coupling reaction based on a copper-free methodology has been applied for the synthesis of conjugated microporous poly(aryleneethynylene) networks (CMPs) from readily available iodoarylenes and 1,3,5-triethynylbenzene. The polymerization reactions were carried out by using equimolar amounts of halogen and terminal alkyne moieties with extremely small loadings of palladium catalyst as low as 0.65 mol %. For the first time, CMPs with rigorously controlled structures were obtained without any indications of side reactions, as proven by FTIR and solid-state NMR spectroscopy, while showing Brunauer-Emmett-Teller (BET) surface areas higher than any poly(aryleneethynylene) network reported before, reaching up to 2552 m2 g-1. A modified one-pot Sonogashira cross-coupling reaction based on a copper-free methodology has been applied for the synthesis of conjugated microporous polymers (CMPs). Not only are the resulting structures much more defined than previously published materials, but they also show far superior Brunauer-Emmett-Teller (BET) surface areas of up to 2552 m2 g-1, setting a new record for this type of materials (see scheme).
- Trunk, Matthias,Herrmann, Anna,Bildirir, Hakan,Yassin, Ali,Schmidt, Johannes,Thomas, Arne
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supporting information
p. 7179 - 7183
(2016/05/24)
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- Size-controlled synthesis of conjugated polymer nanoparticles in confined nanoreactors
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Soluble conjugated polymeric nanoparticles are synthesized by Suzuki-type polycondensation of two monomers (Ax + By, x>2, y≥2) in the channel of ordered mesoporous silica-supported carbon nano-membranes (nanoreactors). These synthesized soluble conjugated microporous polymers (SCMPs) exhibit uniform particle-size distributions and well-controlled particle sizes. The control of particle size stems from the fact that the polycondensations exclusively take place inside the mesochannels of the nano-reactors. Photo-luminescence studies show that polymeric nanoparticles with tetraphenylethene and pyrene substructures are highly fluorescent. The combination of both physical stability and process-ability offered by the soluble polymeric nanoparticles makes them particularly attractive in light emitting and other optoelectronic applications.
- Deng, Sheng,Zhi, Jian,Zhang, Xianmei,Wu, Qingqing,Ding, Yun,Hu, Aiguo
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supporting information
p. 14144 - 14148
(2015/02/19)
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- Polyfluorinated functionalized m-terphenyls. New substituents and ligands in organometallic synthesis
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The synthesis and structural characterization of polyfluorinated arenes 2,4,6-(C6F5)3C6H2X and 2,6-(C6F5)2-4-BrC6H2X (X = NO2, Cl, Br) obtained in the Ullmann-type cross coupling reaction is reported. The nitro derivatives were reduced to the aromatic amines. The α-diimine [2,4,6-(C6F5)3C 6H2NCMe]2 and 2,4,6-(C6F 5)3C6H2I were obtained in condensation and Sandmeyer reactions, respectively, from the corresponding amine. The syntheses of 2,4,6-(C6F5)3C 6H2NHC(O)H, 2,4,6-(C6F5) 3C6H2NC, and 2,4,6-(C6F 5)3C6H2Si(X)Me2 (X = H, F, Cl) are also described.
- Olaru, Marian,Beckmann, Jens,Rat, Ciprian I.
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p. 3012 - 3020
(2014/07/08)
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- Optically active, amphiphilic poly(meta -phenylene ethynylene)s: Synthesis, hydrogen-bonding enforced helix stability, and direct AFM observation of their helical structures
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Optically active, amphiphilic poly(meta-phenylene ethynylene)s (PPEa) bearing l- or d-alanine-derived oligo(ethylene glycol) side chains connected to the backbone via amide linkages were prepared by microwave-assisted polycondensation. PPEa's exhibited an intense Cotton effect in the π-conjugated main-chain chromophore regions in various polar and nonpolar organic solvents due to a predominantly one-handed helical conformation stabilized by an intramolecular hydrogen-bonding network between the amide groups of the pendants. The stable helical structure was retained in the bulk and led to supramolecular column formation from stacked helices in oriented polymer films as evidenced by X-ray diffraction. Atomic force microscopy was used to directly visualize the helical structures of the polymers in two-dimensional crystalline layers with molecular resolution, and, for the first time, their absolute helical senses could unambiguously be determined.
- Banno, Motonori,Yamaguchi, Tomoko,Nagai, Kanji,Kaiser, Christian,Hecht, Stefan,Yashima, Eiji
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supporting information; experimental part
p. 8718 - 8728
(2012/06/30)
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- Facile aromatic finkelstein iodination (AFI) reaction in 1,3-dimethyl-2-imidazolidinone (DMI)
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In this communication, we report the superior role of 1,3-dimethyl-2- imidazolidinone (DMI) as a solvent for aromatic Finkelstein iodination (AFI), the conversion of aryl bromides to aryl iodides. DMI accelerates the reaction rate and affords product(s) that could not be prepared using previous methods. Our findings for AFI avoid the use of toxic solvents such as N,N-dimethylformamide and hexamethylphosphoramide. Taylor & Francis Group, LLC.
- Yamashita, Ken-Ichi,Tsuboi, Michihiro,Asano, Motoko S.,Sugiura, Ken-Ichi
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experimental part
p. 170 - 175
(2011/11/29)
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- Synthesis of oligosilyldi- and trianions
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1,3- and 1,4-Bis[tris(trimethylsilyl)silylethynyl]benzenes as well as 1,3,5-tris[tris(trimethylsilyl)silylethynyl]benzene were synthesized employing Sonogashira cross-coupling conditions. All three molecules underwent facile di- or trimetalation with potassium tert-butoxide to afford the respective oligosilyldi- and trianions.
- Mechtler, Christian,Zirngast, Michaela,Gaderbauer, Walter,Wallner, Andreas,Baumgartner, Judith,Marschner, Christoph
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p. 150 - 158
(2007/10/03)
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- Oligofunctional amphiphiles featuring geometric core group preorganization: Synthesis and study of Langmuir and Langmuir-Blodgett films
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Based on the principle of supramolecular preorganization, a new type of oligofunctional amphiphile, of which compounds 1-4 are representative structures, has been designed and synthesized. The typical feature of their structure is a highly rigid and geometrically well-defined central unit composed of ethynylene substituted aromatic spacers with different numbers of amphiphilic segment groups (also of a rigid geometric design) attached to it. The molecules form well-defined Langmuir films when spread from a solution at the air/water interface or when a 10-4 M aqueous CaCl2 solution was used as the subphase. By analysis of the surface pressure-surface area (π-A) isotherms, information on the packing behavior and orientation of the amphiphilic molecules depending on the molecular structure could be obtained. Morphological characterization of the dynamic process of monolayer compression at the air/water interface was carried out by Brewster angle microscopy, illustrating several phase states visualized as snap shots. Thin monolayer films produced on a 10-4 M aqueous CaCl2 subphase can be transferred to a mica solid support by the Langmuir-Blodgett technique. Tapping mode atomic force microscopy reveals a surface topography of the monofilms composed of 1 and 3 that differ in roughness and also in the properties of elasticity, hardness and adhesive strength. X-Ray crystal structure analysis of three relevant intermediate compounds of the synthesis were successfully determined giving an indication of the potential structural features inherent in the new amphiphiles. The Royal Society of Chemistry 2005.
- Mueller, Petra U.,Weber, Edwin,Rheinwald, Gerd,Seichter, Wilhelm
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p. 3757 - 3766
(2007/10/03)
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- Synthesis of diiodo- and triiodoanilines by iodination of aniline with potassium dichloroiodate and preparation of 1,3,5-triiodobenzene
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A new chemoselective procedure was developed for the synthesis of 2,4,6-triiodoaniline and 2,4-diiodoaniline by the reaction of aniline with potassium dichloroiodate in dilute HCl. Subsequent deamination of 2,4,6-triiodoaniline afforded 1,3,5-triiodobenzene in good yield.
- Vatsadze,Titanyuk,Chernikov,Zyk
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p. 471 - 473
(2007/10/03)
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- Synthesis of carbon dendron nano-chains with π-extended conjugation based on linear 1,4-phenylethynyl and 1,5-naphthylethynyl subunits
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A convenient and efficient synthesis of 3,5-di(trimethylsilylethynyl)phenylacetylene and p-[3,5-di(trimethylsilylethynyl)-1-phenylethynyl]phenylacetylene and the naphthylethynyl homologues terminal acetylenes of 5-(N,N-dimethylamino)naphthylethyne have been carried out. These terminal acetylene compounds serve to prepare nanometer-sized conjugated 1,3,5-tri(ethynylphenyl)benzene and 1,3,5-tri(ethynylnaphthyl)benzene oligomers, by means of heterocoupling with 1,3,5-triiodobenzene, catalysed by palladium, in excellent yields. Both the ethynylphenyl or ethynylnaphthyl homologues chains show fluorescence emission radiation, with important quantum yield.
- Rodríguez, J. Gonzalo,Tejedor, J. Luis,Esquivias, Jorge,Díaz, Cristina
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p. 6375 - 6378
(2007/10/03)
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- Synthesis and optical properties of conjugated dendrimers with unsymmetrical branching
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An improved synthetic approach to conjugated monodendrons with unsymmetrical branching structures is reported. Dendrimers containing two or three such conjugated monodendrons are synthesized and their optical properties are studied. Such dendrimers exhibit broad absorptions and very high fluorescence quantum yields, making them promising candidates for applications in molecular-based photonics.
- Pan, Yongchun,Peng, Zhonghua,Melinger, Joseph S.
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p. 5495 - 5506
(2007/10/03)
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- Synthesis of low generation phenylenealkylene dendrons as nonpolar building blocks for a dendrimer construction set
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The gram scale syntheses of first and second generation (G1 and G2) dendrons 1-4, and 35, based on aryl and alkyl moieties, by Suzuki-Miyaura cross-coupling are presented. Both a divergent and an accelerated convergent route are applied. In addition, first results on the synthesis of hyperbranched oligomers of AB2 monomer 19 are reported.
- Beinhoff, Matthias,Karakaya, Birol,Schlüter, A. Dieter
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- Synthesis of nanostructures based on 1,4- and 1,3,5-ethynylphenyl subunits with π-extended conjugation. Carbon dendron units
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Nanometer-sized conjugated 1,4- and 1,3,5-ethynylphenyl oligomers were synthesized starting from 3,5-di(trimethylsilylethynyl)phenylacetylene and p-[3,5-di(trimethylsilylethynyl)-1-ethynylphenyl]-phenyl acetylene by cross-coupling reaction with a convenient haloaryl derivative, catalyzed by palladium(II)/copper(I), in excellent yield. The terminal acetylenes were efficiently prepared by a specific protection-deprotection methodology. All ethynylphenyl homologues obtained show fluorescence emission, with the bathochromic shift of approximately 20 nm by each ethynylphenyl unit increasing the conjugate chain. Parallel conjugated ethynylphenyl chains were prepared through the insertion of a 1,5-naphthalene subunit, and the compounds exhibit fluorescence radiation emission.
- Gonzalo Rodriguez,Esquivias, Jorge,Lafuente, Antonio,Diaz, Cristina
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p. 8120 - 8128
(2007/10/03)
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- Sialoside clusters as potential ligands for siglecs (sialoadhesins)
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Clusters of O- and S-linked α-sialosides with valencies of two to four were constructed to serve as potential multivalent inhibitors towards sialoadhesins (siglecs). Thus, O- and S-prop-2-ynyl α-sialosides (3, 7), together with 4-iodophenyl sialoside 5 were prepared from acetochloroneuraminic acid derivative 1 using silver salicylate and propargyl alcohol for 3 and phase-transfer catalysis for 5 and 7, respectively. Oxidative acetylenic homocoupling of 3 and 7 under Glaser conditions (CuCl, O2) provided 1,3-diynes 8 and 9 in 83-86% yields. Palladium catalyzed cross-coupling of O-prop-2-ynyl sialoside 3 with 5 using Pd2(dba)3 and PPh3 gave nonsymmetrical dimer 10 (82%). Alternatively, symmetrical clusters were then prepared as above under Sonogashira cross-coupling conditions with 1,4-diiodobenzene (11), 1,3,5-triodobenzene (14), and finally 1,2,4,6-tetraiodobenzene (17) to provide both O- and S-linked dimers 12 (93%) and 13 (88%), trimers 15 (81%) and 16 (76%), while only O-linked tetramer 18 was prepared in 87% yield. Finally, treatment of the O-linked prop-2-ynyl sialoside 3 with Grubbs' metathesis catalyst Cl2Ru(PCy3)2=CHPh (19) gave, as expected, benzeneannulation regioisomeric trimers 20a, 20b in 68% yield.
- Gan, Zhonghong,Roy, Rene
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p. 908 - 916
(2007/10/03)
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- EPR probes with well-defined, long distances between two or three unpaired electrons
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The synthesis of rod- and star-shaped compounds carrying two or three spin labels as end groups is described. The unpaired electrons are 2.8-5.1 nm apart from each other. The shape-persistent scaffolds were obtained through Pd-Cu-catalyzed alkynyl-aryl coupling and Pd-Cu-catalyzed, alkyne dimerization in the presence of oxygen using p-phenyleneethynylene as the basic shape-persistent building block. The spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-carboxylic acid (4) was attached through esterification of the terminal phenolic OH groups of the scaffold.
- Godt,Franzen,Veit,Enkelmann,Pannier,Jeschke
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p. 7575 - 7582
(2007/10/03)
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- High-spin polyphenoxyls attached to star-shaped poly(phenylenevinylene)s
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Star-shaped poly(1,2-phenylenevinylene)s 4-substituted with multiple pendant phenoxyls (2 and 3) were synthesized by polymerizing 2-bromo-4-(acetoxyphenyl)styrene in the presence of 1,3,5-triiodobenzene or 1,3,5-tris(3′,5′-diiodophenyl)benzene as the core via a simple one-pot Heck reaction and subsequent hydrolysis, phenolate formation, and heterogeneous oxidation. ESR spectra indicated a delocalized spin distribution into the core parts of the star-shaped molecules. The polyradicals, 2 and 3, were in a high-spin state at low temperature, and the ferromagnetic behavior was enhanced for the polyradical with a higher molecular weight. Although an average S of 3 remained at 3/2 to 4/2, the polyradical 2 even with a spin concentration of 0.8 spin/unit revealed an average S of 7/2 to 8/2. The 1,3,5-benzene core acted as an effective magnetic coupler to align the spins of the pendant phenoxyls through the star-shaped π-conjugated backbone.
- Nishide, Hiroyuki,Miyasaka, Makoto,Tsuchida, Eishun
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p. 7399 - 7407
(2007/10/03)
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- Toward a hexagonal grid polymer: Synthesis, coupling, and chemically reversible surface-pinning of the star connectors, 1,3,5- C6H3(CB10H10CX)3
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A synthetic approach to a two-dimensional grid polymer is proposed and the execution of initial steps is described. Pd-catalyzed coupling of (1,12- dicarba-closo-dodecaboran-1-yl)copper (10) with iodobenzene, m-diiodobenzene, and 1,3,5-triiodobenzene yielded the known 1,12-dicarba-closo-dodecaboran-1- ylbenzene (3) and the new m-bis(1,12-dicarba-closo-dodecaboran-1-yl)benzene (4) and 1,3,5-tris(1,12-dicarba-closo-dodecaboran-1-yl)benzene (1), respectively. Each arm of the trigonal connector 1 was provided with one or two sticky tentacles by conversion to 1,3,5-tris[12-((3- (ethylthio)propyl)dimethylsilyl)-1,12-dicarba-closo-dodecaboran-1-yl]benzene (7) and 1,3,5-tris[12-(bis(3-(ethylthio)propyl)methylsilyl)-1,12-dicarba- closo-dodecaboran-1-yl]benzene (8). Linear coupling of carboranyl CH terminals through a mercury atom produced very stable dimeric structures from 3 and 4. The carborane 3, its mercury-linked dimer 13, the 1:1 complex of 13 with 2,2'-bipyridyl, and the 2:1 complex of 13 with 2,2'-bipyrimidyl have been structurally characterized by single-crystal X-ray crystallography, but crystals of 1 showed an intriguing disorder and could not be used for molecular structure determination. Grazing incidence IR spectra show that the tentacled species 7 and 8 adsorb firmly on the surface of gold, apparently without a strong preference for a particular orientation. At room temperature, the tritentacled species 7 can be removed readily and the hexatentacled species 8 more slowly by treatment with a THF solution containing fluoride, which severs the tentacles.
- Sch?berl, Ulrich,Magnera, Thomas F.,Harrison, Robin M.,Fleischer, Frank,Pflug, Jodi L.,Schwab, Peter F. H.,Meng, Xiangsheng,Lipiak, Dariusz,Noll, Bruce C.,Allured, Viloya S.,Rudalevige, Trevor,Lee, Stephen,Michl, Josef
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p. 3907 - 3917
(2007/10/03)
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- 2-phenyl-carbapenems
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Carbapenems of the formula STR1 are useful intermediates to antibacterial agents.
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- Syntheses and Spectral Properties of Several Branched-chain Polyphenyls containing 1,3,5-Trisubstituted Ring(s)
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Six polyphenyls, including four new compounds, 5',5''-di(2-biphenylyl)-2,2'''-diphenyl-m-quaterphenyl (3), 2,5',2''-triphenyl-m-terphenyl (4), 3,5-di(2-biphenylyl)-o-terphenyl (5), and 5''-(3-biphenylyl)-m-quinquephenyl (6), were synthesized by the Ullmann coupling reaction of iodo compounds.Proton magnetic resonance spectral studies indicated that the characteristic spectral features of the polyphenyls containing 1,3,5-trisubstituted ring system(s) were fully compatible with their conformational aspects deduced from stereomodels.Ultraviolet spectral data indicated that the dihedral angle of the pivot bond of the branched ring in the polyphenyls in solution is very similar to that of biphenyl.Keywords - Ullmann reaction; quinquephenyl; sexiphenyl; septiphenyl; decaphenyl; polyphenyl; IR; UV; 1H-NMR
- Ozasa, Shigeru,Fujioka, Yasuhiro,Hashino, Hiromi,Kimura, Naoko,Ibuki, Eiichi
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p. 2313 - 2320
(2007/10/02)
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