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Exocyclic Stereocontrol via Asymmetric Hydrovinylation in the General Synthesis of Pseudopterogorgia Natural Products Stereoselective X-Y-Mediated Cyclization Studies of an Allene-Ynamide and an Allene-AldehydeMans, Daniel J. 18 March 2008 (has links)
No description available.
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Gold catalysis: stereoselective synthesis of propargylamines and axially chiral allenes, and application on naturalproduct modificationsLo, Kar-yan., 盧嘉茵. January 2009 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Substituent Effects: A Computational Study on Stabilities of Cumulenes and Low Barrier Hydrogen BondsKumar, Ganesh Angusamy 08 1900 (has links)
The effect of substituents on the stabilities of cumulenes-ketenes, allenes, diazomethanes and isocyanates and related systems-alkynes, nitriles and nitrile oxides is studied using the density functional theory (B3LYP, SVWN and BP86) and ab initio (HF, MP2) calculations at the 6-31G* basis set level. Using isodesmic reactions, correlation between stabilization energies of cumulenes and substituent group electronegativities (c BE) is established and the results from DFT and MP2 methods are compared with the earlier HF calculations. Calculations revealed that the density functional methods can be used to study the effect of substituents on the stabilities of cumulenes. It is observed that the cumulenes are stabilized by electropositive substituent groups from s -electron donation and p -electron withdrawal and are destabilized by electronegative substituent groups from n-p donation. The calculated geometries of the cumulenes are compared with the available experimental data.High level ab initio and density functional theory calculations have been used to study the energetics of low-barrier hydrogen bond (LBHB) systems. Using substituted formic acid-formate anion complexes as model LBHB systems, hydrogen bond strength is correlated to the pKa mismatch between the hydrogen bond donor and the hydrogen bond acceptor. LBHB model systems are characterized by the 1H-NMR chemical shift calculations. A linear correlation between the calculated hydrogen bond strength and the predicted 1H-NMR chemical shift was established. It is concluded that the pKa matching within the enzyme active site of the two species involved in the LBHB is important to maximizing catalytic stabilization.
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Gold catalysis stereoselective synthesis of propargylamines and axially chiral allenes, and application on natural product modifications /Lo, Kar-yan. January 2009 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references. Also available in print.
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Synthese van allenylmetaal-reagentia en hun regioselectieve omzetting in functioneel gesubstitueerde allenen, alkynen en enige heterocycli Synthesis of allenymetal reagents and their regioselective conversion into functionally substituted allenes, alkynes, and some heterocycles /Ruitenberg, Klaas, January 1983 (has links)
Thesis (doctoral)--Rijksuniversiteit te Utrecht, 1983. / Summary in English. Spine title: Allenylmetaal-reagentia en hun omzetting in allenen, allynen en enige heterocycli. Additional references inserted. Description based on print version record. Includes vita and bibliographies.
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Reaction of allene with phenyl azideKhattak, Rangin Khan 01 January 1974 (has links)
The purpose of this work was to investigate the reaction of allena and phenyl azide, in order to gain greater insight into the reaction of aryl azides with allenes.
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PYRIDONE PHOTOCYCLOADDITION IN SYNTHESIS OF DIVERSE NATURAL AND UNNATURAL PRODUCTSKulyk, Svitlana January 2014 (has links)
2-Pyridones are known to undergo a facile [4+4] photocycloaddition with themselves and other conjugated molecules. These transformations provide an access to complex molecular structures such as highly substituted cyclooctanoid derivatives, which normally represent a significant synthetic challenge. Moreover, the 2-pyridone photoadducts can be further elaborated into various biologically relevant products. The work presented here broadens the horizons of the [4+4] photocycloaddition in two distinct directions: 1) by utilizing [4+4] photocycloaddition in a total synthesis of crinipellin natural products possessing antibiotic and antitumor activity and 2) by developing a novel type of [4+4] photocycloaddition that employs a conjugated enyne as a partner of 2- pyridone. Our approach to the tetraquinane core of the crinipellins features intramolecular [4+4] photocycloaddition of a tethered furan-pyridone molecule followed by a four-step transannular ring closure. The sequence allows for a rapid assembly of a molecular framework by installing 19 of the 20 required carbon atoms and all but two stereogenic centers. The described synthesis represents an interesting new approach to these polycyclic molecules and a way to access crinipellin analogues. The enyne-pyridone [4+4] photocycloaddition led to formation of intriguing 1,2,5-cyclooctatriene-based products. Presence of the allene functionality was used as a lever in exploring the possibilities for derivatization of these photoadducts. Our investigations of enyne-pyridone photocycloaddition have come a long way: from the first proof-of-concept intermolecular trials producing complex mixtures, through the initial investigations of the intramolecular variant that taught us how to direct the reaction to the necessary mode ([2+2] vs. [4+4] photocycloaddition), and eventually to the controlled formation of stable allenic photoadducts and their further transformation into a diverse set of functionalized molecular scaffolds. We found that the inherent kinetic instability of 1,2,5-cyclooctatrienes facilitates several pathways of strain relief: allene-allene [2+2] dimerization, photooxidative decarbonylation when the irradiation is conducted in presence of air, isomerization of the 1,2-diene fragment into a 1,3-diene and the acid-promoted Cope rearrangement. Additionally, enyne-pyridone photoadducts can undergo transannular ring closure when treated with bromine and also be transformed into valuable bicyclo [5.1.0] octane structures that incorporate a rare example of a stable cyclopropanone by a fast and selective epoxidation-rearrangement process. Several important goals were achieved in the described research study. First, strategic incorporation of [4+4] photocycloaddition as one of the key steps in targeted synthesis of natural products has demonstrated the potential of this powerful reaction. Second, an efficient new approach to a tetraquinane skeleton was developed and successfully executed. Third, the fundamental basis for the novel photochemical transformation (enyne-pyridone cycloaddition) was set and major trends for this reaction were established resulting in obtaining stable allenic photoadducts. Finally, chemical properties and reactivity of stabilized amide-bridged 1,2,5-cyclooctatriene photoproducts were investigated breaking the ground for future involvement of these intermediates in synthetic strategies towards biologically active natural products and their analogues. / Chemistry
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Discovery of Novel Fatty Acid Dioxygenases and Cytochromes P450 : Mechanisms of Oxylipin Biosynthesis in Pathogenic FungiHoffmann, Inga January 2013 (has links)
Dioxygenase-cytochrome P450 (DOX-CYP) fusion enzymes are present in diverse human and plant pathogenic fungi. They oxygenate fatty acids to lipid mediators which have regulatory functions in fungal development and toxin production. These enzymes catalyze the formation of fatty acid hydroperoxides which are subsequently converted by the P450 activities or reduced to the corresponding alcohols. The N-terminal DOX domains show catalytic and structural homology to mammalian cyclooxygenases, which belong to the most thoroughly studied human enzymes. 7,8-Linoleate diol synthase (LDS) of the plant pathogenic fungus Gaeumannomyces graminis was the first characterized member of the DOX-CYP fusion enzyme family. It catalyzes the conversion of linoleic acid to 8R-hydroperoxylinoleic acid (HPODE) and subsequently to 7S,8S-dihydroxylinoleic acid by its DOX and P450 domains, respectively. By now, several enzymes with homology to 7,8-LDS have been identified in important fungi, e.g., psi factor-producing oxygenase (ppo)A, ppoB, and ppoC, of Aspergillus nidulans and A. fumigatus. By cloning and recombinant expression, ppoA of A. fumigatus was identified as 5,8-LDS. Partial expression of the 8R-DOX domains of 5,8-LDS of A. fumigatus and 7,8-LDS of G. graminis yielded active protein which demonstrates that the DOX activities of LDS are independent of their P450 domains. The latter domains were shown to contain a conserved motif with catalytically important amide residues. As judged by site-directed mutagenesis studies, 5,8- and 7,8-LDS seem to facilitate heterolytic cleavage of the oxygen-oxygen bond of 8R-HPODE by aid of a glutamine and an asparagine residue, respectively. Cloning and expression of putative DOX-CYP fusion proteins of A. terreus and Fusarium oxysporum led to the discovery of novel enzyme activities, e.g., linoleate 9S-DOX and two allene oxide synthases (AOS), specific for 9R- and 9S-HPODE, respectively. The fungal AOS are present in the P450 domains of two DOX-CYP fusion enzymes and show higher sequence homology to LDS than to plant AOS and constitute therefore a novel class of AOS. In summary, this thesis describes the discovery of novel fatty acid oxygenases of human and plant pathogenic fungi and the characterization of their reaction mechanisms.
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Reactive and inelastic processes in the gas-phase at ultra-low temperaturesChastaing, Delphine January 2000 (has links)
No description available.
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Transition metal catalyzed hydrogenative and transfer hydrogenative C-C bond formationSkucas, Eduardas 24 August 2010 (has links)
Carbon-carbon bond formation is one the fundamental reactions in organic
synthesis. The quest for the development of new and more efficient processes for the
construction of this bond has been an ongoing focus for years. The transformations that
permit the use of simple precursors to access complex structural architectures in the
absence of stoichiometric quantities by-products are highly desirable.
Hydrogen is a cheapest and cleanest reductant available to the mankind. The
catalytic hydrogenation has been widely utilized in the industry, however the construction
of the carbon-carbon bond under hydrogenative conditions has been achieved only for
alkene hydroformylations and Fisher-Tropsh process and limited to the use of carbon
monoxide. The extension of the hydrogenative carbon-carbon bond formations beyond
aforementioned processes would be of a great significance to the synthetic community.
The overview of allene use in the metal catalyzed reactions to achieve carbonyl
and imine allylation and vinylation is presented in Chapter 1. The following chapter
vii
discusses the development of metal catalyzed hydrogenative and transfer hydrogenative
coupling of allenes and carbonyl compounds to afford allylation products. These studies
have resulted in the development of the first carbonyl allylation from the alcohol
oxidation level. Chapter 3 discusses efforts towards achieving highly enantioselective
hydrogenative coupling of alkynes to carbonyl compounds. / text
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