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Showing 1 to 20 of 57 for “"diastereomer"”.
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Rhodium-katalysierte, asymmetrische Synthese: Ligandendesign und Methodik
… or the Walphos family furnished the exo-diastereomer predominantly and with up to 82% ee. In contrast, the use of monodentate ligands such as the phosphoramidite MonoPhos™ led diastereoselectively to the endo-diastereomer with up to 54% ee. Initial experiments with bidentate …
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Understanding the Solid State, Solubility and Dissolution Behavior of Cefuroxime Axetil Diastereomers in Interactive Mixture Formulations
… present in commercial products as a mixture of diastereomers, which commonly form eutectic mixtures. A phase diagram was constructed utilizing differential scanning calorimetry. It was observed that the diastereomers formed a eutectic mixture with a composition of 75% isomer B and a melting …
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Stereochemical Effect of RAFT Agents on Kinetics of Reversible Deactivation Radical Polymerization
… chains. In this thesis, two ideal models (diastereomeric macro-RAFT agents with different chemical structures and two inherent diastereomers for each) were designed and prepared by single unit monomer insertion (SUMI) technology to examine their stereochemical effect on kinetics of RDRP. In …
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Investigation of ligand misdirection using the kinetic element effect and the kinetic enthalpy effect.
… and [(eta6-C6H6)Ru(dabp)(Cl)]+. Only one diastereomer was observed for [Ru(bipy)2(dabp)] 2+ in the 1H NMR spectrum. Exchange was observed and measured for the ruthenium and osmium complexes of [(eta6-C 6H6)M(dabp)(Cl)]+.
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The enantioselective synthesis of C₁₈-sphingosines
… via the selective preparation of the appropriate diastereomer of azido alcohol (118), were C-4 and C-5 correspond to C-3 and C-2 of the sphingosine skeleton, respectively (Scheme 1).
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The Synthesis-Enabled Stereochemical Elucidation of the Marine Natural Products Hemicalide and Phormidolide A
… C16-C25 and C35-C46 fragments to a single diastereomer with reasonable confidence. However, the relative configuration between fragments and the absolute stereochemistry remains unknown. Part II describes the synthesis of the C16-C28 dihydroxylactone fragment, which was used to successfully …
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Total Syntheses of 1,2,4-Thiadiazole Natural Products
… to form natural products 24a and 24b, along with diastereomer 144a/b. The result of the biomimetic thio-Diels-Alder reaction was supported by DFT analysis and corroborated the postulate made in the original report that the C-2' alcohol of (±)-31 is too distant from the forming spirocentre to exert …
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I. Catalyst development in asymmetric phase transfer catalysis employing QSAR methods II. Computational investigations on the stereochemical course of the addition of allylsilanes to aldehydes
… manifold. The selectivity for the syn diastereomer in the electrophilic activation manifolds is accounted for by increased electrostatic and orbital interactions for a particular synclinal transition state at the expense of increased steric interactions relative to antiperiplanar …
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Asymmetrische Totalsynthese von 16(S)-Iloprost und 3-Oxa-16(S)-Iloprost mittels der Azoen-Strategie
… Ventavis registrated iloprost (1:1 mixture of diastereomers at C16) serves as a drug against ischemic heart disease, peripheral vascular disease and primary pulmonary hypertension. The 16S-diastereomer is 5 to 20 times more potent than the 16R-diastereomer in inhibiting collagen-induced …
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Neurotransmitter and Neuromodulator Analysis Using Capillary Electrophoresis With Laser -Induced Fluorescence Detection
… been developed and the D-form dominates in one diastereomer pair. Lastly, in preliminary studies, the release of L-Glu versus acetylcholine from specific regions of the brain of freely moving rats appears dependent on stimulation parameters, causing differential regulation of the circadian …
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Studies Towards the Total Synthesis of Patellazole B
… comparison studies. The synthesis of all eight diastereomers of this macrocycle should aid determination of the four unknown stereocentres. Chapter 2 describes the synthesis of the C1–C12 fragment, focusing on the configuring of the C5 methyl stereocentre and the construction of the C7-C10 …
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Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes
… the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more …
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Advancements in the diastereoselective synthesis of acyl pyrrolidines via the tandem aza-Cope—Mannich cyclization pathway
… oxazolidine starting material as a mixture of diastereomers to produce one pyrrolidine diastereomer. Both ethyland substituted phenyl-oxazolidines were successfully rearranged. This work is the first example of a truly catalytic aza-Cope—Mannich reaction and provides the first examples of …
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Applications of Hypervalent Iodine Reagents: From Enantioselective Copper-Catalysed Arylation-Semipinacol Cascade to Methionine Functionalisation for Peptide Macrocyclisation
… and enantioselectivities, and often as a single diastereomer. These are in turn useful functional handles for transformations into other moieties, including further rearrangements via Baeyer-Villiger oxidation. In the second part of this thesis, a two-step process for the macrocyclisation of …
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Subcomponent self-assembly of cages and mechanically interlocked molecules
… cage, which exists as a mixture of diastereomers at room temperature. Cooling the sample to 253 K results in the selective formation of the S₄-symmetric CuI₆L₄ diastereomer. Changing the solvent from MeCN to DMSO gives a mixture of the S₄-symmetric and T-symmetric diastereomers at …
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The asymmetric synthesis of (2S,3R)-capreomycidine and the total synthesis of capreomycin IB
… trialkyl orthoformate to provide a single diastereomer of the glycinate adduct. Hydrogenolysis provides the optically pure acetal of α-formylglycine. Finally, the total synthesis of capreomyc in IB is described. The synthesis features the incorporation of the previously prepared …
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Donor-Acceptor Cyclobutanes and Their Application for Heterocycle Synthesis and Progress Towards Biselide A
… A. Key reactions for the formation of a single diastereomer of an advanced stage intermediate included: Evans’ asymmetric aldol and a Prasad reduction to form a 1,3-syn diol exclusively which cyclized with Co(nmp)2 in high yield (93%). A tethering strategy will be used for the formation of the …
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Diastereoselective acylation of trans-2-substituted-cyclohexanols and glycosidase inhibition studies
… i.e. produces mixtures of unequal amounts of diastereomers. We found for the first time that addition of pyridine or diisopropylethylamine accelerates the acylation, and unexpectedly for some substituents (RX) may completely invert its diastereoselectivity. These observations have been …
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Theoretical and computational modeling of peptide-lipid bilayer interaction studied by dynamic force spectroscopy
… energetics of the peptide melittin (MWT) and its diastereomer (MD4) interacting with POPC and POPG lipid bilayers. The obtained results provide further insight into the role of secondary structure in peptide-lipid bilayer interactions.
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Applications of 2,3-Diketoesters in Organic Synthesis and Stereoselective Transformations
… catalysis produces the corresponding 1,3-syn diastereomer. The first enantioselective transformation of 2,3-diketoesters was demonstrated in carbonyl-ene reactions catalyzed by [Cu((S,S)-tert-Bu-box)](SbF6)2 generating chiral α-functionalized-α-hydroxy-β-ketoesters in up to 94% yield and 97% …
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