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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
121

A Total Synthesis Of Novel Sesquiterpenoid Natural Product ( ±)-Merrilactone A And A Study Of π-Face Selectivity In Additions To Trigonal Carbon Centers In Iso-Steric Environments

Singh, Sarangthem Robindro 04 1900 (has links)
Natural product synthesis has been a most exciting and challenging branch of organic chemistry in view of its creative power and unlimited scope. Natural product synthesis witnessed an unprecedented growth and innovative developments, especially during the later half of the 20th century. This can be attributed to a number of factors, one of which has been the isolation and characterization of growing number of compounds from natural sources through availability of newer techniques of isolation and purification and advances in the incisive tools (eg. 2D NMR, X-ray, HRMS) of structure determination. Many natural products, though scarce from natural resources, possess wide ranging biological activity and need to be accessed through synthesis for clinical development and evaluation, particularly of analogs. This has been one of the main stimuli in recent years for undertaking the synthesis of natural products. Among the diverse architecture created by Nature, terpenoids are the most variegated in terms of the presence of a bewildering array of carbocyclic frameworks with unusual assemblage of rings and functionalities. This phenomenal structural diversity of terpenoids makes them challenging targets for total synthesis and for the articulation of new synthetic strategies for carbocyclic ring construction. One of the major concerns in organic chemistry, particularly of relevance in synthesis is the control of diastereoselectivity in nucleophilic and electrophilic additions to trigonal carbon atoms as this is the fundamental step in stereogenesis. Several approaches have been devised to achieve diastereoselection and to understand the interplay of underlying stereoelectronic factors. In this context, introduction of newer probe systems and search for incisive interpretations are continuously enriching the area. The present thesis addresses both the above mentioned themes of contemporary interest in organic chemistry and is presented in two main parts. Part-1: A Total Synthesis of Novel Sesquiterpenoid Natural Product (±)-Merrilactone A. Part-2: A Study of -Face Selectivity in Additions to Trigonal Carbon Centers in Iso-steric Environments. The Part-1 describes our travails towards a stereoselective construction of the complex framework present in the biologically potent and structurally novel sesquiterpene natural product Merrilactone A culminating in its total synthesis. The Part-2 narrates the results of -face selectivity in addition reactions to two novel systems, exo-5-subtituted bicyclo[2.1.1]hexan-2-ones, 5-exo-substituted 2-methylene-bicyclo[2.1.1]hexane and 1-substitued tricyclo[2.1.0.02,5]pentan-3-ones, employing various nucleophiles and electrophiles
122

Efforts towards the total synthesis of the stemofoline alkaloids utilizing a novel 1,3-dipolar cycloaddition reaction and application of the Pauson-Khand reaction as a novel entry into bridged azabicyclic ring systems

Shanahan, Charles S. 03 January 2013 (has links)
A novel application of the Pauson-Khand reaction was applied to the synthesis of a series of bridged azatricyclic piperazines. This method represents the first application of the Pauson-Khand reaction to synthesize azabridged scaffolds. The ubiquity of bridged azabicyclic ring systems in biologically active natural product skeletons has provided the synthetic chemist with a wealth of opportunity for development over the last century. To this day, the development of new methodologies to tackle these structurally challenging systems remains at the forefront of synthetic chemistry. During our efforts to achieve a total synthesis of the stemofoline alkaloids, we have thus far developed a novel and scalable synthetic strategy to access the fully functionalized caged azatricyclic core of these challenging alkaloids. The overall synthetic strategy we have implemented began with the commercially available and affordable 2-deoxy-D-ribose as a chiral starting material. Furthermore, we have developed a novel 1,3-dipole cascade cycloaddition, which was successfully employed as the key step in the construction of the bridged azatricyclic core of the stemofoline alkaloids. / text
123

Application of the Moore rearrangement to the synthesis of 1,4-dioxygenated xanthones and efforts toward the total synthesis of lundurine B

Nichols, Alexander Lindsey 31 January 2013 (has links)
A novel application of the Moore rearrangement was successfully developed and applied to the synthesis of 1,4-dioxygenated xanthones that would have been difficult to obtain otherwise. The 1,4-dioxygenated xanthone moiety is found in several naturally occurring, biologically active compounds. Several methods by which to obtain the 1,4-dioxygenated xanthone core have been reported; however, high step counts, low yields, and harsh reaction conditions preclude the use of these methods to complex xanthone natural products. Using the Moore rearrangement as a key step in the synthetic sequence has allowed us to prepare several xanthone natural products quickly and more efficiently than what is possible with the prior art. Using the Martin group’s prior experience with the application of ring closing metathesis (RCM) to the field of alkaloid natural product synthesis, the preparation of lundurine B was undertaken. Key features of the proposed synthesis to lundurine B include the formation of a cyclopropane ring by the formation pyrazoline intermediate via [3+2] dipolar cycloaddition followed by dinitrogen extrusion. A second key step in the proposed sequence to lundurine B is a double RCM to form a five- and eight-membered ring in a single operation. While double RCM strategies have been applied to several elegant natural product syntheses, the formation of a five- and eight-membered ring in a single sequence has not been reported. Should the double RCM strategy prove successful for lundurine B, the conditions could in principle be applied to other structurally related natural products. / text
124

Towards preparative in vitro enzymatic synthesis of new polyketide metabolites

Hughes, Amanda Jane 18 October 2013 (has links)
Modular polyketide synthases (PKSs) are the largest enzymes known to man and are responsible for synthesizing some of the most important human medicines. Their ability to construct stereochemically-rich carbon chains containing diverse substituents has inspired the biosynthetic community to engineer these factories for the in vitro synthesis of a small library of polyketide compounds. New complex polyketides are discovered every year, yet the lack of compound prohibits characterization and testing of these new compounds for medicinal properties. Smaller polyketide compounds generated in vitro could be organically manipulated to generate larger, more complex polyketide natural products and natural product analogs. Chemoenzymatic approaches like this would be extremely beneficial to the scientific community; however, there are still obstacles that must be overcome before the use of PKS for the preparative synthesis of an in vitro generated polyketide library would prove fruitful: purchasing substrates such as methylmalonyl-CoA is cost-prohibitive, PKSs are often difficult to express and purify, and the products generated are typically nonchromophoric. The use of a malonyl-CoA ligase from Streptomyces coelicolor (MatB) was investigated for the enzymatic synthesis of polyketide extender units such as methylmalonyl-CoA (Chapter 2). MatB synthesized a total of 5 CoA-linked extender units in vitro: malonyl-, methylmalonyl-, ethylmalonyl-, hydroxymalonyl- and methoxymalonyl-CoA. Two ternary complex structures of MatB with bound product and leaving group were also solved to sub-2Å resolution. MatB generated extender units were employed in the module-catalyzed synthesis of a triketide pyrone. The selectivity of a PKS module to incorporate a variety of side chains into triketide pyrones was also investigated (Chapter 3). A total of 10 triketide pyrone compounds were synthesized, 5 produced via modular "stuttering" and one possessing a terminal alkyne chemical handle. Lastly, nonchromphoric polyketide products were made visible upon copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) with fluorescent sulforhodamine B azide revealing insights into in vitro reactivites of a PKS module (Chapter 4). The work described in this dissertation has helped advance the scientific community towards procuring an in vitro synthesized polyketide library for future synthetic applications. / text
125

Total Synthesis of Hyperforin

Sparling, Brian Andrew 18 October 2013 (has links)
Hyperforin is the component of the medicinal herb St. John's Wort (Hypericum perforatum) responsible for its antidepressant activity. It works by blocking the reuptake of a variety of neurotransmitters through a unique mechanism of action and may be a critical lead for the treatment of depression and possibly other human diseases. However, the therapeutic potential of hyperforin is severely handicapped by its poor water solubility, facile oxidative degradation, and potent activation of pregnane X receptor, leading to increased expression of many genes involved in xenobiotic metabolism. Access to a wide variety of hyperforin analogs is critical for mitigating these shortcomings while maintaining therapeutic activity. While limited semisynthetic manipulation of isolated hyperforin is feasible, total synthesis is the only possible means of obtaining diverse hyperforin analogs. / Chemistry and Chemical Biology
126

Stereochemistry of Challenging Natural Products Studied by NMR-based Methods

Sun, Han 23 November 2012 (has links)
No description available.
127

A catalytic asymmetric synthesis of palmerolide A

Penner, Marlin Unknown Date
No description available.
128

Transformation Of Cyclohexanone Derivatives To Bicyclic Furan And Pyrrole Derivatives

Yazicioglu, Emre Yusuf 01 August 2004 (has links) (PDF)
Tetrahydrobenzofurans and tetrahydroindoles are two very valuable classes of substances which have wide usage area / either as starting materials for drug substances or many other compounds which have fused heterocyclic rings in their structures and pharmacophore for many complex natural products / syntheses of derivatives of these compounds with different substitution patterns, is an exciting challenge for many scientists. Benzofuran and tetrahydroindole derivatives, which are potent bioactive substances, are synthesized from various cyclohexanone derivatives that are allylated by Stork-enamine or Mn(OAc)3 mediated allylation methods. Allylated ketones are later transformed to benzofuran derivatives upon treatment with base or tetrahydroindole derivatives upon treatment with primary amines.
129

Biomimetic Orientated Total Synthesis of Neovibsane Natural Products and Comparison of Synthetic Neovibsanes on Neurite Outgrowth Promotion in PC12 Cells

Annette Chen Unknown Date (has links)
Neovibsanin A and B are natural products which induced neurite outgrowth in PC12 cells. They belong in the neovibsane class under the rare vibsane natural product family, whose structures are characterized by polycyclic, polyoxygenated cores. Based on a proposed biosynthesis, the synthetic strategy towards neovibsanin A and B involved synthesizing a key enone intermediate. Initial investigation using this intermediate lead to the total synthesis of 2-O-methylneovibsanin H. Crucial to this concise synthesis was an acid-catalyzed, one-pot, four-step cascade reaction. Modifying the reaction condition leads to a different five-step cascade pathway, resulting in the total synthesis of 4,5-bis-epi-neovibsanin A and B. The synthetic trials and tribulations encountered on the road to these final compounds are explored. It is envisaged that other related neovibsane natural products may arise based on this synthetic sequence. 4,5-Bis-epi-neovibsanin A and B, as well as several other structural analogues collected during the synthesis, were biologically assayed using NGF-stimulated PC12 cells. All compounds induced a significant proportion of neurons to extend neurite processes compared to control cultures. The structure-activity relationship studies indicated that the tricyclic core, as well as the 3,3-dimethylacroyl enol ester side chain, may be responsible for promoting a biological response.
130

2-Iodoxybenzoic Acid: Acidity Investigations and The Total Synthesis of 5,14-bis-epi-Spirovibsanin A

Mr Michael Gallen Unknown Date (has links)
No description available.

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