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81.
This paper describes the stereoselective outcome of the intramolecular Diels-Alder furan (IMDAF) reaction of substituted (2S,3S)-ethanolamides 9-13, which were synthesised from a furyl substituted cyanohydrin. The latter was obtained from 2-furaldehyde with high enantioselectivity by an oxynitrilase catalysed addition of hydrogen cyanide. The stereochemistry of the IMDAF products was shown to be dependent on the size of the ethanolamide substituents R. Small substituents (H, Me, CN) gave exclusively exo-cycloaddition, whereas more bulky ones (Ph, Et) gave both evo- and endo-addition, the larger phenyl substituent giving a high endo-exo-ratio. 相似文献
82.
Johannes Reisch Anura Wickramasinghe 《Monatshefte für Chemie / Chemical Monthly》1990,121(8-9):709-712
Summary Epoxidation of the acridone alkaloid acronycine (1) resulted in hydroxylation at the aromatic ring giving 5-hydroxyacronycine (3). The same reaction on 1,3-dimethoxy-10-methyl-9(10H)-acridinone (5) gave 1,3-dimethoxy-2-hydroxy-10-methyl-9(10H)-acridinone (6), 1,3-dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)-acridinone (8), and 1,3-dimethoxy-2,4-diperoxy-10-methyl-9(10H)-acridinone (9).
Naturstoffchemie, 137. Mitt.: Oxidierung von Acridonalkaloiden: Synthese des 5-Methoxyacronycins (Kurze Mitt.)
Zusammenfassung Die Epoxidierung des Acridonalkaloids Acronycin führte zu einer Hydroxylierung des aromatischen Rings, wobei 5-Hydroxyacronycin (3) entstand. Die gleiche Reaktion mit 1,3-Dimethoxy-10-methyl-9(10H)acridinon (5) ergab 1,3-Dimethoxy-2-hydroxy-10-methyl-9(10H)acridinon (6), 1,3-Dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)acridinon (8) und 1,3-Dimethoxy-2,4-diperoxy-10-methyl-9(10H)acridinon (9).相似文献
83.
Penicillamine Complexes of Nickel, Chromium, and Molybdenum — Structural Particularity and Biological/Medical Relevance The compounds Tl2[NiII(H2O)6][NiII(D-pen)(L-pen)]2[NiII(SCN)2(H2O)4] 1 , Tl[NiII(D-pen)2H] · H2O 2 , Tl[CrIII(D-pen)2] 3 , and Na2[MoO4(pen)2] · 3 CH3OH · 3 H2O 4 have been prepared by the reaction of nickel nitrate (for 1 ), nickel acetate (for 2 ), potassium chromate (for 3 ), and sodium molybdate (for 4 ) with D- and D, L-penicillamine, respectively. They were characterized by single-crystal X-ray structure analysis and other physical methods. Whereas penicillamine acts as a bidentate (N, S)-ligand in 1 and 2 , CrIII (in 3 ), and MoV (in 4 ) are coordinated to the three ligand atoms N, O, and S. The presence of three different types of NiII-complexes a cationic, a neutral, and an anionic one in 1 is remarkable. For crystal data see Inhaltsübersicht. 相似文献
84.
Matthias Treu Christian Hametner Johannes Frohlich Ulrich Jordis Kurt Mereiter 《Journal of heterocyclic chemistry》2002,39(6):1283-1288
The synthesis of a novel unnatural carbocyclic analog of the acetylcholine esterase inhibitor galanthamine with a K3[Fe(CN)6] promoted oxidative tandem cyclization as the key step is reported. 相似文献
85.
86.
René Csuk Johannes Haas Helmut Hönig Hans Weidmann 《Monatshefte für Chemie / Chemical Monthly》1981,112(6-7):879-882
A synthesis of new boron containingMannich bases of salicylamide by reaction of salicylamide, formaldehyde and boron-heterocycles is reported.
VIII. Mitteilung:Stump, R. K., Zimmerman jr., H. K., Schleppnik, A. A., Gutsche, C. D., Liebigs Ann. Chem.667, 18 (1963). 相似文献
87.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
88.
Chlorocarbenium salts
-
of the Vilsmeier-Arnold type react with the silylated isocyanuric acid
to give 1-oxa-3-azabutatrienium salts
under mild conditions. From reactions of diarylchloromethenium salts
-
with
and ketones or tertiary carboxamides high yields of 2-azaallenium salts
were obtained. A few chloro substituted 2-azaallenium salts
were prepared from
and carbonyl compounds. The mechanisms of the new reactions are discussed. 相似文献
89.
Molybdenum cofactor (Moco) deficiency (MoCD) is characterized by neonatal-onset myoclonic epileptic encephalopathy and dystonia with cerebral MRI changes similar to hypoxic–ischemic lesions. The molecular cause of the disease is the loss of sulfite oxidase (SOX) activity, one of four Moco-dependent enzymes in men. Accumulating toxic sulfite causes a secondary increase of metabolites such as S-sulfocysteine and thiosulfate as well as a decrease in cysteine and its oxidized form, cystine. Moco is synthesized by a three-step biosynthetic pathway that involves the gene products of MOCS1, MOCS2, MOCS3, and GPHN. Depending on which synthetic step is impaired, MoCD is classified as type A, B, or C. This distinction is relevant for patient management because the metabolic block in MoCD type A can be circumvented by administering cyclic pyranopterin monophosphate (cPMP). Substitution therapy with cPMP is highly effective in reducing sulfite toxicity and restoring biochemical homeostasis, while the clinical outcome critically depends on the degree of brain injury prior to the start of treatment. In the absence of a specific treatment for MoCD type B/C and SOX deficiency, we summarize recent progress in our understanding of the underlying metabolic changes in cysteine homeostasis and propose novel therapeutic interventions to circumvent those pathological changes. 相似文献
90.
Lorenzo Estivi Luisa Pellegrino Johannes A. Hogenboom Andrea Brandolini Alyssa Hidalgo 《Molecules (Basel, Switzerland)》2022,27(21)
A viable approach to improve the nutritional quality of cereal-based foods is their enrichment with pseudocereals. The aim of this research was to evaluate the antioxidant properties of amaranth, quinoa and buckwheat, and the heat damage of water biscuits (WB) produced from either wholemeal or refined flour of einkorn and enriched with 50% buckwheat, amaranth or quinoa wholemeal. Buckwheat had the highest tocols content (86.2 mg/kg), and einkorn the most carotenoids (5.6 mg/kg). Conjugated phenolics concentration was highest in buckwheat (230.2 mg/kg) and quinoa (218.6 mg/kg), while bound phenolics content was greatest in einkorn (712.5 mg/kg) and bread wheat (675.7 mg/kg). The all-wholemeal WB had greater heat damage than those containing refined flour (furosine: 251.5 vs. 235.8 mg/100 g protein; glucosylisomaltol: 1.0 vs. 0.6 mg/kg DM; hydroxymethylfurfural: 4.3 vs. 2.8 mg/kg DM; furfural: 8.6 vs. 4.8 mg/kg DM). The 100% bread wheat and einkorn wholemeal WB showed greater heat damage than the WB with pseudocereals (furfural, 9.2 vs. 5.1 mg/kg; glucosylisomaltol 1.1 vs. 0.7 mg/kg). Despite a superior lysine loss, the amino-acid profile of the pseudocereals-enriched WB remained more balanced compared to that of the wheats WB. 相似文献