- Chemoenzymatic Halocyclization of γ,δ-Unsaturated Carboxylic Acids and Alcohols
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A chemoenzymatic method for the halocyclization of unsaturated alcohols and acids by using the robust V-dependent chloroperoxidase from Curvularia inaequalis (CiVCPO) as catalyst has been developed for the in situ generation of hypohalites. A broad range of halolactones and cyclic haloethers are formed with excellent performance of the biocatalyst.
- Younes, Sabry H. H.,Tieves, Florian,Lan, Dongming,Wang, Yonghua,Süss, Philipp,Brundiek, Henrike,Wever, Ron,Hollmann, Frank
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- Self-assembly and solid-state polymerization of butadiyne derivatives with amide and trialkoxyphenyl groups
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Three butadiyne derivatives with amide and tri(dodecyloxy)-phenyl (TDP) groups were synthesized, and four solidification methods were applied to obtain their self-assembling states in various conditions. The solids obtained were characterized by the solid-state polymerization behaviors, stretching vibration wavenumbers of N-H bonds of amide groups, powder X-ray diffraction, the thermal behaviors, and scanning electron microscope (SEM) observations. We found that all compounds had at least two polymorphs. Property differences between two polymorphs depended on the compounds. Two compounds showed clear differences in UV-vis spectra of the photo-polymerized solids, i.e., the polydiacetylene (PDA) structure, and irregularly polymerized form, or two PDA structures. The remaining compound showed the same PDA absorption but the monomer melting points were different. All compounds gave the gels in various organic solvents because of the molecular design with amide and TDP groups. SEM observation clarified the relationship between gel appearance and the nanostructures.
- Kikuchi, Kohei,Tatewaki, Yoko,Okada, Shuji
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supporting information
p. 298 - 305
(2017/05/10)
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- Synthesis and solid-state polymerization of a macrocyclic compound with two butadiyne units
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A macrocyclic compound 1 with two butadiyne and four dodecyloxy-substituted benzamide moieties was successfully synthesized, and its ring structure was confirmed by the MALDI-TOF mass spectra and the 1HNMR spectra. Compound 1 showed two modifications depending on solvent for the solidification. Characteristic excitonic absorption bands of polydiacetylene were observed at around 500 nm for one of the modifications after UV irradiation. Quantitative conversion of butadiyne moieties to the corresponding polydiacetylene structure was confirmed by the Raman spectra.
- Kikuchi, Kohei,Tatewaki, Yoko,Okada, Shuji
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p. 387 - 394
(2017/06/14)
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- Arylation of [6,6]-spiroacetal enol ethers: Reactivity and rearrangement
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Attempts to selectively arylate [6,6]-spiroacetal enol ethers at the 2-position delivered unexpected results. Palladium-mediated arylation conditions afforded the double-Heck product, whereas reaction with benzenesulfinic acid resulted in a facile rearrangement into the corresponding 5-phenylsulfonyl-3,4, 5,6-tetrahydrochromans, providing access to 5-aryl-3,4,5,6-tetrahydrochroman and hexahydrochroman derivatives.
- Aumann, Kylee M.,Healy, Peter C.,Coster, Mark J.
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supporting information; experimental part
p. 1070 - 1073
(2011/03/22)
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- Efficient synthesis of 8,11-dimethylene-bicyclo[5.3.1]undecan-2-one
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We report here, an effective methodology for the preparation of 8,11-dimethylene-bicyclo[5.3.1]undecan-2-one. The key steps in these reactions were chloromethylation, cationic-alkyne cyclization and anionic fragmentation sequence.
- Gu, Haining,Xu, Wei Ming,Kinstle, Thomas H.
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p. 6449 - 6451
(2007/10/03)
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- Synthesis haptens and development of an immunoassay for the olive fruit fly pheromone
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An enzyme-linked immunosorbent assay (ELISA) for the olive fruit fly pheromone, Bactrocera oleae Gmelin, was developed. The assay uses polyclonal antibodies, raised in rabbits, against (±)-β-[3-(1,7-dioxaspiro[5.5] undecane)]propionic acid, 2 (hapten I), conjugated to the KLH (keyhole limpet hemocyanin) by the carbodiimide method. A second hapten, (±)-δ-[3- (1,7-dioxaspiro[5.5]undecane)]-butylamine, 3 (hapten II), after conjugation to a biotin moiety, was used for indirect immobilization onto ELISA microwells precoated with the glycoprotein avidin. The developed ELISA method measures the synthetic olive fruit fly pheromone in concentrations ranging between 0.08 and 10 μg/mL and shows great promise for practical applications for pheromone detection in environmental and biological samples. The results obtained strongly indicate that this technique, to our knowledge the first insect pheromone enzyme-linked immunosorbent assay so far reported, is a fast, sensitive, inexpensive, and highly convenient method for the analysis of a volatile and low molecular weight compound such as 1,7-dioxaspiro[5.5]undecane, 1.
- Neokosmidi, Afroditi,Ragoussis, Valentine,Zikos, Christos,Paravatou-Petsotas, Maria,Livaniou, Evangelia,Ragoussis, Nikitas,Evangelatos, Gregory
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p. 4368 - 4374
(2007/10/03)
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- Stereoselective total syntheses of 9(S)- and 9(R)-HETE
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A simple and efficient stereoselective total synthesis of methyl 9(S)- and 9(R)-hydroxy -5(Z), 7(E), 11(Z), 14(Z)-eicosatetraenoates using base induced opening of chiral 2.3-epoxy chlorides is described.
- Yadav,Bhanu,Dutta, Dinah
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p. 3929 - 3934
(2007/10/03)
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- A Stereoselective Synthesis of 8(R) and 8(S), 11(R),12(S)-Trihydroxyeicosa-5(Z),9(E),14(Z)-Trienoic Acid from 2-Deoxy-D-Ribose
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A stereoselective synthesis of stereoisomers of the title compound from 2-deoxy-D-ribose using reductive elimination protocol as the key step is described.
- Yadav, J. S.,Vadapalli, Prahlad
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p. 641 - 644
(2007/10/02)
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- A new simple and industrial process for bromination of alcohols
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Alcohols treated with thionylchloride, followed by chlorine/bromine exchange using gaseous hydrobromic acid and thermal decomposition in the presence of a tertiary amine give the corresponding brominated compounds. The process is regio/stereo selective.
- Mas,Metivier
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p. 2187 - 2191
(2007/10/02)
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- Single Electron Transfer Mechanism in the Reaction of 1,3-Dithianyllithium and Alkyl Iodides
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The reaction between 2-lithio-1,3-dithiane and optically active (R)-2-iodooctane was found to proceed with complete inversion of configuration.This result suggests that the SN2 (rather than single electron transfer (SET)) mechanism is the preferred pathway for reaction between dithianyllithium and unhindered alkyl halides.When the neopentyl-type radical probe 5,5-dimethyl-6-iodo-1-hexene was used as the substrate halide, 6-11percent cyclized alkylated product was obtained.This result suggests that when the SN2 pathway is blocked, SET mechanisms become operative to some extent, at least with iodide as the halogen.The reaction of dithianyllithium and (R)-2-iodooctane and 5,5-dimethyl-6-iodo-1-hexene, with hexane as the solvent, proceeds under heterogeneous conditions to bring about complete racemization of the respective iodide.These results demonstrate for the first time that 2-lithio-1,3-dithiane can act as electron donor in reactions initiated by electron transfer to alkyl iodides.
- Juaristi, Eusebio,Jimenez-Vazquez, Hugo A.
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p. 1623 - 1630
(2007/10/02)
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- SYNTHESE ET REACTIVITE DE SILANES PROPARGYLIQUES ω-FONCTIONNELS : PREPARATION DE VINYLIDENE-3 OXOLANNES, OXANNES, OXEPANNES ET OXOCANNES
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The ω-silyloxypropargyltrimethylsilanes regiospecifically react with aliphatic and aromatic aldehydes to lead to vinylidene oxigen-containing heterocycles, such as 3-vinylidene oxolanes, oxanes, oxepanes and oxocanes.
- Pornet, J.,Damour, D.,Miginiac, L.
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p. 2017 - 2024
(2007/10/02)
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- Intramolecular Addition of Alkoxy Radicals. Part 4. Reductive Cyclisation of Olefinic Hydroperoxides
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Pent-4-enyl hydroperoxide reacts with reducing salts (FeX2, TiCl3) to afford tetrahydrofurfuryl compounds (halides or dimers) in high yield from the selective cyclisation of the pent-4-enyloxy radical.Analogous behaviour is observed for photolysis although the yields of cyclic products are lower.The photolysis of hex-5-enyl hydroperoxide does not yield cyclic products but these are observed when this hydroperoxide is reduced by FeCl2.It is suggested that metallic salts are able to complex the alkoxyl radicals thereby making them more electrophilic and hence more prone to cyclise.
- Taillez, Bernard,Bertrand, Michele Paula,Surzur, Jean-Marie
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p. 547 - 554
(2007/10/02)
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