Physical Sciences and Mathematics Commons^™

Dechalcogenative Allylic Selenosulfide And Disulfide Rearrangements For Cysteine Modification And Glycoligation, Venkataraman Subramanian

Wayne State University Dissertations

This thesis describes investigations directed at the development of methods for the selenosulfide and disulfide rearrangements for the permanent functionalization of thiols, and in particular of cysteine and carbohydrate based thiols. Emphasis is placed on the newly invented silver mediated allylic desulfurative rearrangement for the primary modification of thiols and the synthesis of complex oligosaccharide mimics.

Chapter one introduces the concept of chemoselective ligations for the modification of macromolecules like carbohydrates and proteins. It overviews the native and non-native ligation techniques for their modification of such entities with a attention focusing on thiol based ligation techniques. The later part of …

Synthesis Of Functionalized Gpi Anchors And Related Glycoconjugates, Benjamin M. Swarts

Wayne State University Dissertations

This dissertation is divided into two chapters describing the background, significance, and synthesis of GPI anchors and GPI-anchored molecules. GPI anchors are a class of complex glycolipids with the primary purpose of attaching cell surface proteins/glycoproteins to the cell membrane. The first chapter is focused on the synthesis of functionalized GPI anchors, and begins with an introductory look at the discovery, structure, biosynthesis, and biological functions of GPIs. Then, after surveying progress and achievements in GPI synthesis, including discussion about current strategic shortcomings in the field that prevent the chemical synthesis of various GPI derivatives, our approach to accessing uniquely …

I-Kinetic And Mechanistic Investigations Of Amino Acid Substrates Reactivities With Ferryl Species, Ahmed Ibrahim Youssef Abouelatta

Wayne State University Dissertations

ABSTRACT

I-KINETIC AND MECHANISTIC INVESTIGATIONS OF AMINO ACID SUBSTRATES REACTIVITIES WITH FERRYL SPECIES

II-SYNTHESIS AND CHARACTERIZATION OF DERIVATIVES OF THE BN-TPEN LIGAND AND THEIR METAL COMPLEXES

by

AHMED IBRAHIM YOUSSEF ABOUELATTA

MAY 2011

Advisor: Dr. Jeremy Jacob Kodanko

Major: Chemistry (Organic)

Degree: Doctor of philosophy

The reactivity of tryptophan, methionine, aspartic acid, glutamic acid, histidine and hydrochloride salt of lysine amino acid substrates with the N4Py ferryl species was studied by UV-vis spectroscopy and product characterization. Based on kinetic isotope effect studies and product analysis, an ET-PT mechanism was proposed for the reaction of tryptophan substrate with N4Py ferryl and …

Transition Metal-Mediated Higher-Order Cycloaddition Reactions: Application To The Total Synthesis Of Complex Natural Products, Bilal Abou Aleiwi

Wayne State University Dissertations

ABSTRACT

TRANSITION METAL-MEDIATED HIGHER-ORDER CYCLOADDITION REACTIONS: APPLICATION TO THE TOTAL SYNTHESIS OF COMPLEX NATURAL PRODUCTS

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BILAL ABOU ALEIWI

October 2010

Advisor: Dr. James H. Rigby

Major: Chemistry (Organic)

Degree: Doctor of Philosophy

Chromium (0)-mediated [6ð + 2ð] and [6ð + 2ð + 2ð] cycloaddition reactions between cyclic trienes and alkynes is reported. The development, investigation and the application of these reactions in the total synthesis of complex ring systems and natural products is described. Two natural products, namely, ∆ 9(12) -Capnellene and Echinopines A and B were targeted.

An investigation led to the successful development of a methodology to …

A Bioarchaeological Study Of A Prehistoric Michigan Population: Fraaer-Tyra Site (20sa9), Allison June Muhammad

Wayne State University Dissertations

ABSTRACT

The Saginaw Valley Region has been the focus of Michigan archaeology for many decades. The Late Woodland period of the Saginaw Valley has been characterized as an area that prehistoric people abandoned as a permanent resident, but exploited seasonally during times of scarcity. Furthermore, the valley's resources were exploited by a diverse group of prehistoric peoples, both native to Michigan and those Mississippian `intruders' (Halsey 1976; Holman and Brashler 1999; Norder et al. 2003; Stothers 1999). Though previous studies of the Frazer-Tyra site (20SA9) have included ceramic and lithic analysis (Andrews 1995; Halsey 1976) and a study of mortuary …

I. Microwave-Influenced Diversity-Oriented Synthesis Of Biologically Relevant Small & Natural-Product-Like Molecules Via Multicomponent Coupling Reactions Ii. Synthetic Studies Toward The Total Synthesis Of The Repeating Tetrasaccharide Unit Of Zwitterionic Polysaccharide Ps A1, Soumava Santra

Wayne State University Dissertations

Microwave-influenced diversity-oriented synthesis of biologically relevant small and natural-product-like molecules via multicomponent coupling reactions (MCCRs) have been investigated. Cheap, readily available starting materials in conjunction of microwave irradiation and employment of environmentally benign solvent (e.g. water) provided a common platform that allowed to access a wide array of structurally and skeletally diverse molecules. The investigation allowed us to establish a new paradigm of diversity-activity relationships (DARs) by tuning reacting components of the MCCRs and proved that in contrary to the conventional use of microwave as a rate accelerating tool, it can be used to influence reactivity of molecules. The method …

Development And Applications Of Thioacids In Peptide Chemistry And Exploration Of Methods Toward The Stereochemical Elucidation And Synthesis Of Virgineone, Kasinath Sana

Wayne State University Dissertations

ABSTRACT

DEVELOPMENT AND APPLICATIONS OF THIOACIDS IN PEPTIDE CHEMISTRY AND EXPLORATION OF METHODS TOWARD THE STEREOCHEMICAL ELUCIDATION AND SYNTHESIS OF VIRGINEONE

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KASINATH SANA

December 2010

Advisor: David Crich

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation describes investigations toward the development of methods for the synthesis of peptidyl thioacids and thioesters, with particular emphasis on applications in peptide chemistry, and the exploration of methods toward the assignment of the relative and absolute configuration of virgineone and its total synthesis.

The first part of chapter one introduces the general characteristics and reactivity of thioacids, and describes their potential for application …