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1.
Aryl sulfides were obtained from the coupling reaction of S-aryl (or S-alkyl) thioacetates and aryl bromides in the presence of palladium catalyst. This reaction method enables the one-pot synthesis of symmetrical and unsymmetrical diaryl sulfides by employing potassium thioacetate with aryl iodides and aryl bromides. 相似文献
2.
We present here an easy, rapid copper-free methodology for the Sonogashira coupling reaction. It works well for a range of aryl iodides and activated aryl bromides. 相似文献
3.
The combination of palladium chloride with BINAP shows high efficiency in the decarboxylative cross-coupling reactions of arenecarboxylic acids with aryl iodides. The reactions proceed smoothly to generate the corresponding biaryl compounds in good to excellent yields. 相似文献
4.
Jessing M Brandt M Jensen KJ Christensen JB Boas U 《The Journal of organic chemistry》2006,71(18):6734-6741
Solid-phase synthesis is of tremendous importance for small-molecule and biopolymer synthesis. Linkers (handles) that release amide-containing products after completion of solid-phase synthesis are widely used. Here we present a new class of highly acid-labile backbone amide linkers (BAL handles) based on 3,4-ethylenedioxythiophene (EDOT), which we have termed T-BAL. These thiophene linkers are synthesized in three convenient steps from commercially available EDOT. In the linker design, the spacer was introduced to the EDOT core either via a carbon-carbon bond or via a thioether linkage. Introduction of the spacer via a C-C bond was performed by a chemoselective Negishi coupling without transient protection of the aldehyde group to provide the T-BAL1 handle. Introduction via a thioether linkage was performed by a facile nucleophilic aromatic substitution between the brominated EDOT aldehyde and unprotected mercapto acids to provide T-BAL2 and T-BAL3 handles. The minimal use of protecting groups gave the corresponding linker molecules in few synthetic steps and in good yields. After anchoring of the linker to a polymeric support, introduction of the first amino acid was achieved by reductive amination, giving a secondary amine. A following acylation of the secondary amine with a symmetrical amino acid anhydride resulted in a backbone amide linkage between the handle and the growing substrate (e.g., peptide chain). After solid-phase synthesis, the substrates could be released from the resin by either low acid conditions using 1% TFA in CH2Cl2 or high acid conditions such as 50% TFA in CH2Cl2. Peptide thioesters could be released from the T-BAL1 handle under very mild conditions using aqueous acetic acid. Tert-butyl based protecting groups, tert-butyl esters, tert-butyl ethers, and Boc groups, as well as dimethyl acetals were relatively stable to these mild conditions for release of the peptides. 相似文献
5.
A ligand-free nickel-catalyzed Kumada cross-coupling of aryl bromides and tert-butyl Grignard reagents led to the formation of a series of tert-butyl aryls in moderate to good yields, excellent tBu/iBu ratios, and good functional group compatibility. A radical coupling process is indicated and a mechanism with a Ni(I)-Ni(III) catalytic cycle is proposed. 相似文献
6.
Yuichiro Tokoro Atsushi Nagai Yoshiki Chujo 《Journal of polymer science. Part A, Polymer chemistry》2010,48(16):3693-3701
New organoboron aminoquinolate‐based polymers linked by π‐conjugated bridge were prepared by Sonogashira–Hagihara coupling of organoboron aminoquinolate‐based bisiodo monomers bearing biphenyl or bithiophene moiety with 1,4‐diethynylbenzene derivatives. Tetracoordination states of boron atoms in the obtained polymers were confirmed by 11B NMR spectroscopy, and they were also characterized by 1H NMR and IR spectroscopies and size‐exclusion chromatography. Their optical properties were studied by UV–vis absorption and photoluminescence spectroscopies. In the region above 400 nm, the polymers prepared from 1,4‐diethynyl‐2,5‐dioctyloxybenzene showed bathochromic shifts when compared with those prepared from 1.4‐diethynyl‐2‐perfluorooctyl‐5‐trifluoromethylbenzene. The polymers with biphenyl moiety showed higher absolute fluorescence quantum yields (?F = 0.28 and 0.65), whereas those with bithiophene moiety led to decreasing of the low quantum yields (?F = 0.19 and 0.00). The density‐functional theory (DFT) and time‐dependent–DFT calculations of model compounds corresponding to the polymers were in good agreement with the results from UV–vis properties. The calculations revealed that the electronic structure of the polymer with bithiophene moiety is different from that with biphenyl moiety, and predicted the electron transfer from the bithiophene moiety to the π‐extended quinoline moiety in transition state. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3693–3701, 2010 相似文献
7.
A new two-step four-component synthesis of highly functionalized cyclohexenols by sequential nickel-catalyzed couplings 总被引:1,自引:0,他引:1
A new two-step procedure for the synthesis of cyclohexenols has been developed. A nickel-catalyzed three-component addition of an enal, alkyne, and acetylenic tin affords substituted hept-4-en-6-ynals. The products of this first step then undergo a second nickel-catalyzed reaction with organozincs or organoboranes to afford densely functionalized cyclohexenols. Variation in each of the four components is tolerated to provide access to a wide range of versatile building blocks. 相似文献
8.
Alkynyl carboxylic acids reacted with aryl iodides under a CO atmosphere in the presence of a palladium catalyst to produce α,β-alkynyl aryl ketones in good yields. The maximum turnover number was 16?800. The desired carbonylative coupling was formed from phenyl propiolic acid without any formation of a noncarbonylative coupling product in the absence of CuI. However, the reaction with alkyl-substituted alkynyl carboxylic acids required CuI as a cocatalyst for high yield. 相似文献
9.
Aromatic azides with hindered amine light stabilizer (HALS) residues or hydrophilic groups such as glucose, sucrose and dextrine residues were synthesized and used for surface modification of polyolefins. By UV‐irradiation nitrenes were formed, which are able to react with polyolefin surfaces. By photochemical immobilization of the carbohydrates hydrophilicity of PE and PP was strongly increased (surface tensions > 44mN/m). Light stability of PP surfaces modified with HALS azides was comparable with PP, stabilised with Tinuvin 770. Bulk modification of ethylene‐propylene and ethylene‐octene copolymers was achieved by grafting nitrenes formed by thermal decomposition of azido benzoic acid. In a circulating air oven up to 1.55 wt% amino benzoic acid residues could be bonded covalently to ethylene‐propylene‐copolymers, less than half of it to ethylene‐octene‐copolymers. Reactive extrusion resulted in grafting yields of more than 50% for both types of copolymers. 相似文献
10.
The organolithium species derived from proton abstraction of N-Boc-piperidine with s-BuLi and TMEDA can be transmetalated to the organozinc reagent, and this organometallic species can be coupled directly with aryl bromides in a Negishi-type reaction using palladium catalysis with the ligand tri-tert-butylphosphine (t-Bu3P-HBF4). The chemistry was applied to a very short synthesis of the alkaloid anabasine. 相似文献
11.
Novel enzyme activities and functional plasticity revealed by recombining highly homologous enzymes 总被引:13,自引:0,他引:13
Raillard S Krebber A Chen Y Ness JE Bermudez E Trinidad R Fullem R Davis C Welch M Seffernick J Wackett LP Stemmer WP Minshull J 《Chemistry & biology》2001,8(9):891-898
BACKGROUND: Directed evolution by DNA shuffling has been used to modify physical and catalytic properties of biological systems. We have shuffled two highly homologous triazine hydrolases and conducted an exploration of the substrate specificities of the resulting enzymes to acquire a better understanding of the possible distributions of novel functions in sequence space. RESULTS: Both parental enzymes and a library of 1600 variant triazine hydrolases were screened against a synthetic library of 15 triazines. The shuffled library contained enzymes with up to 150-fold greater transformation rates than either parent. It also contained enzymes that hydrolyzed five of eight triazines that were not substrates for either starting enzyme. CONCLUSIONS: Permutation of nine amino acid differences resulted in a set of enzymes with surprisingly diverse patterns of reactions catalyzed. The functional richness of this small area of sequence space may aid our understanding of both natural and artificial evolution. 相似文献
12.
The so-called SPhos phosphine, an extremely active ligand in the amination and Suzuki coupling of sterically-hindered aryl chlorides, has been anchored on different supports such as non-soluble (cross-linked polystyrene) and soluble (non-cross-linked polystyrene and polyethyleneglycol) polymers, as well as high surface silica. SPhos anchored on polyethyleneglycol (PEG-SPhos) showed the best activity for both amination and Suzuki couplings. The PEG-SPhos ligand can be quantitatively recovered from the reaction mixture through precipitation with diethyl ether and recycled in four consecutive runs without loosing activity. 31P NMR spectra of the reused anchored ligand showed that deactivation of the PEG-SPhos ligand comes from the progressive oxidation of the phosphine-to-phosphine oxide. 相似文献
13.
Karvembu Ramasamy Jayabalakrishnan Chinnasamy Dharmaraj Nallasamy Renukadevi Somanur V. Natarajan Karuppannan 《Transition Metal Chemistry》2002,27(6):631-638
Binuclear ruthenium(III) complexes containing a binucleating Schiff base ligand, L and Ph3P or Ph3As, [RuX2(EPh3)2]2L (X = Cl or Br; E = P or As) have been prepared by reacting [RuCl3(PPh3)3], [RuCl3(AsPh3)3], [RuBr3(AsPh3)3] and [RuBr3(PPh3)2(MeOH)] with Schiff bases in a 2:1 molar ratio. The Schiff bases used in this study were prepared by condensing the appropriate diamine with salicylaldehyde or benzoylacetone in a 1:2 molar ratio respectively. The complexes were characterised by analytical, spectral (i.r., electronic, e.p.r.) and electrochemical data. An octahedral structure has been proposed for all the new ligand-bridged binuclear RuIII complexes. The new complexes have been used as catalysts in aryl–aryl couplings and also subjected to antifungal activity studies. 相似文献
14.
Ionic liquid-promoted, highly regioselective Heck arylation of electron-rich olefins by aryl halides
Palladium-catalyzed regioselective Heck arylation of the electron-rich olefins, vinyl ethers 1a-d, enamides 1e-g, and allyltrimethylsilane 1h, has been accomplished in imidazolium ionic liquids with a wide range of aryl bromides and iodides instead of the commonly used, but commercially unavailable and expensive, aryl triflates. The reaction proceeded with high efficiency and remarkable regioselectivity without the need for costly or toxic halide scavengers, leading exclusively to substitution by aryl groups of diverse electronic and steric properties at the olefinic carbon alpha to the heteroatom of 1a-g and beta to the heteroatom of 1h. In contrast, the arylation reaction in molecular solvents led to mixtures of regioisomers under similar conditions. Several lines of evidence point to the unique regiocontrol stemming from the ionic environment provided by the ionic liquid that alters the reaction pathway. The chemistry provides a simple, effective method for preparing branched, arylated olefins and contributes to the extension of Heck reaction to a wider range of substrates. 相似文献
15.
Mamdouh W Uji-i H Ladislaw JS Dulcey AE Percec V De Schryver FC De Feyter S 《Journal of the American Chemical Society》2006,128(1):317-325
The effect of solvent on the two-dimensional (2D) supramolecular ordering of monodendron 1 at the liquid-solid interface has been systematically investigated by means of scanning tunneling microscopy (STM). Solvents range from those with hydrophilic solvating properties, such as alkylated alcohols and acids, to hydrophobic solvents such as alkylated aromatics and alkanes. Dramatic differences in the 2D ordering are observed depending on the nature of the solvent. Of particular interest is the fact that in hydrophobic solvating solvents, such as aliphatic and aromatic hydrocarbons, solvent molecules are coadsorbed in the 2D molecular network while this is not the case for alkylated alcohols or acids. Furthermore, in the case of the coadsorbing solvents, a striking influence of the alkyl chain length has been observed on the 2D pattern formed. The solvent and alkyl chain length dependences are discussed in terms of molecule-molecule interactions (homo and hetero) and molecule-substrate interactions. 相似文献
16.
Kyungho ParkGoun Bae Ahbyeol ParkYong Kim Jaehoon ChoeKwang Ho Song Sunwoo Lee 《Tetrahedron letters》2011,52(5):576-580
Symmetric diarylalkynes were obtained from the decarboxylative coupling reactions of aryl bromides and propiolic acid in water solvent condition. In the presence of phase transfer surfactant C18H37N(CH3)3Cl, the catalytic system of both Pd(PPh3)2Cl2/dppb and Pd(TPPMS)2Cl2/TPPMS afforded the desired coupled products in good yields. 相似文献
17.
Viswanathan R Smith CR Prabhakaran EN Johnston JN 《The Journal of organic chemistry》2008,73(8):3040-3046
5-exo-trig Cyclization of an aryl radical to the nitrogen of an azomethine is used as the key annulating step in a modular preparation of 2,3-cis- and trans-disubstituted indolines. The precursors are readily prepared by phase-transfer-catalyzed Michael addition of a glycine Schiff base to a variety of acceptors. When the more reactive alkylidene malonate Michael acceptors are implemented, a one-pot three-component coupling is possible. The net result is a convergent [3 + 2] coupling strategy for the construction of highly functionalized indolines, a substructure occurring in numerous biologically active natural products. 相似文献
18.
Cross-coupling reactions between lipophilic terminal alkynes and aryl bromides can be catalyzed by ligated Pd, in the absence of copper, in pure water at ambient temperatures. Small amounts of the nonionic amphiphile PTS assist by virtue of nanometer micelles formed spontaneously in an aqueous medium. 相似文献
19.
Midya GC Paladhi S Dhara K Dash J 《Chemical communications (Cambridge, England)》2011,47(23):6698-6700
Iron can catalyze head-to-head dimerization of terminal aryl alkynes to give the corresponding (E) selective conjugated enynes in high yields. A variety of substituted aryl acetylenes underwent smooth dimerization using catalytic FeCl(3) and DMEDA in the presence of KO(t)Bu. 相似文献