Search results for "Hydrogenolysis"
showing 10 items of 15 documents
Stereoselective Synthesis of (+)-11βH,13-Dihydroestafiatin, (+)-11βH,13-Dihydroludartin, (−)-Compressanolide, and (−)-11βH,13-Dihydromicheliolide fro…
2002
Starting from 2 and 3, obtained from santonin (1), we have synthesized natural guaianolides 4-7. Chemoselective epoxidation of 2 gave (+)-11betaH,13-dihydroestafiatin (4), and epoxidation of 3 followed by regioselective elimination of the hydroxyl group afforded (+)-11betaH,13-dihydroludartin (5). Sharpless' mild regioselective ring-opening of 4 and 5 followed by hydrogenolysis yielded (-)-compressanolide (6) and (-)-11betaH,13-dihydromicheliolide (7), respectively.
Trapping AsPh3 via reaction with NiS/γ-Al2O3 in the presence of H2: Reaction mechanism and kinetics
2021
International audience; Removal of As from petroleum feedstocks is an important process which can be realized using As trapping mass containing supported nickel sulfide. In order to understand the mechanism of the trapping we studied the reaction of AsPh3 with NiS/γ-Al2O3 in the presence of H2 in a batch reactor in toluene solution at 230 °C. This reaction results in formation of NiAs, benzene and H2S. Also, the intermediate species, thiophenol and diphenylsulfide, were observed. Despite formation of NiAs layer in the course of reaction, the rate of AsPh3 decomposition is not affected by the solid state diffusion up to ∼ 50 % of nickel conversion. The rate determining step in these conditio…
Die Synthese vono-Acylamino-β-dimethylamino-propiophenonen. 4. Mitt.: Synthese der primären Mannich-Basen
1972
Das durch Umsetzung von 2-Acetamino-β-dimethylamino-propiophenon (IVb) mit Dibenzylamin darstellbare 2-Acetamino-β-dibenzylamino-propiophenon (XXVII) kann hydrogenolytisch mit tels Palladium-Aktivkohle in die entsprechende, nur am aromatischen Stickstoff acetylierte primare Mannich-Base ubergefuhrt werden. In analoger Weise sind auch in 5-Stellung substituierte Derivate des 2-Acetamino-β-amino-propiophenons (XXVIII) zuganglich. Synthesis of 2-Acylamino-β-amino-propiophenones 2-Acetamino-β-dibenzylamino-propiophenone (XXVII) and its derivatives, substituted in 5-position, can be synthetized by reaction of 2-acetamino-β-dimethylamino-propiophenone (IVb) with dibenzylamine. By hydrogenolysis i…
Hydrogenolysis of carbon–carbon σ-bonds using water catalysed by semi-rigid diiridium(iii) porphyrins
2019
Semi-rigid diiridium(III) porphyrin alkyls with m-xylyl and p-xylyl diether linkers were synthesized. They were found to be catalysts for the carbon–carbon σ-bond hydrogenolysis of [2.2]paracyclophane under neutral conditions using water as the hydrogen source. The ether linkages in semi-rigid diiridium(III) porphyrins are unstable and undergo cleavage during the reaction.
Redox-Responsive Block Copolymers: Poly(vinylferrocene)-b-poly(lactide) Diblock and Miktoarm Star Polymers and Their Behavior in Solution
2013
The synthesis of diblock and miktoarm star polymers containing poly(vinylferrocene) (PVFc) and poly(l-lactide) (PLA) blocks is introduced. End functionalization of PVFc was carried out via end capping of living carbanionic PVFc chains with benzyl glycidyl ether (BGE). By hydrogenolysis of the benzyl protecting group a dihydroxyl end-functionalized PVFc was obtained. Both monohydroxyl- and dihydroxyl-functionalized PVFcs have been utilized as macroinitiators for the subsequent polymerization of l-lactide via catalytic ring-opening polymerization. A series of block copolymers and AB2 miktoarm star polymers was synthesized with varied PLA chain lengths. All polymers were characterized in detai…
New syntheses of condensed heterocycles from isoxazole derivatives. V. Pyrrolo[3,4-b]pyridin-4-ones
1977
Hydrogenolysis with Raney-Nickel or iron powder in acetic acid of 2,5-diphenyl-4-nitro-3-(3,5-R,R-4-isoxazolyl)pyrrolyl ketones, prepared by the Grignard reaction of 2,5-diphenylpyrrole and 3,5-R,R-4-isoxazolecarboxilic acid chlorides followed by nitration, afforded directly the desired 6H-pyrrolo[3,4-b ]pyridin-4-ones.
Water-Soluble Poly(vinylferrocene)-b-Poly(ethylene oxide) Diblock and Miktoarm Star Polymers
2012
We describe the synthesis of water-soluble diblock and miktoarm star polymers consisting of poly(vinylferrocene) (PVFc) and poly(ethylene oxide) (PEO) blocks. First, end-functionalized poly(vinylferrocene) was generated by end-capping the living carbanionic PVFc chains with benzyl glycidyl ether (BGE) or ethoxy ethyl glycidyl ether (EEGE). Acidic hydrolysis of the EEGE-terminated PVFc partially oxidized the PVFc backbone. However, the dihydroxyl end-functional PVFc was obtained in quantitative yields by hydrogenolysis of the BGE-terminated PVFc. A series of block copolymers and AB2 miktoarm star copolymers was obtained in a second polymerization step, utilizing the respective end-functional…
Hydrogenolysis of hydroxymatairesinol on Y derived catalysts: a computational study
2010
Hydrogenolysis of 7-hydroxymatairesinol (HMR) to matairesinol (MAT) occurs on palladium supported acidic catalysts. HMR has three stereochemical centres and naturally exists as a mixture of two diastereoisomers, namely RRR-HMR and SRR-HMR. The latter is significantly more reactive than the former, in the reaction above. In order to elucidate the hydrogenolysis mechanism, simple surface events involving HMR derivatives on aluminated faujasite (H-Y) fragments were simulated by quantum chemical calculations. The metallic function of a Pd/H-Y acidic catalyst was also mimicked by a minimal palladium cluster. Stereochemical evidences pointed already out that water β-elimination on the epimeric ce…
Free and bound hydroxyl and carboxyl groups in the cutin of Quercus suber leaves
1984
Abstract The number of free and bound hydroxyl and carboxyl groups of the cutin of Quercus suber leaves was investigated by the lithium borohydride hydrogenolysis of mesyl-cutin compared with the lithium borohydride hydrogenolysis of untreated cutin. Fifty per cent of the vic -diol groups of the trihydroxy C 18 acid component and twenty five per cent of the secondary hydroxyl groups of the dihydroxy C 16 acid component are free. The rest of the secondary and all of the primary hydroxyl groups are esterified; all carboxyl groups are esterified.
Single-Component Polymerization Catalysts for Ethylene and Styrene: Synthesis, Characterization, and Reactivity of Alkyl and Hydrido Yttrium Complex…
1999
Yttrium alkyl complexes Y(η5:η1-C5Me4SiMe2NCMe2R)(CH2SiMe3)(THF) (R = Me, Et) and Y(η5:η1-C9H6SiMe2NCMe3)(CH2SiMe3)(THF) can be prepared in high yields by a σ-bond metathesis reaction between Y(CH2SiMe3)3(THF)2 and amino-functionalized cyclopentadienes or indene. The structure of Y(η5:η1-C5Me4SiMe2NCMe2Et)(CH2SiMe3)(THF) was shown by single-crystal X-ray diffraction to be that of a three-legged piano stool. Reaction of Y(CH2SiMe3)3(THF)2 with the tridentate linked amido−cyclopentadienyl ligands (C5Me4H)SiMe2NHR (R = CH2CH2OMe, CH2CH2NMe2, CH2CH2CH2OMe, CMe2CH2OMe), which contain an additional donor site, results in the cleavage of the silicon−cyclopentadienyl bond and the formation of the t…