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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.
31

Reactions of anthocyanins and o-quinones in model systems and foods

Afanas'yev, Dmytro Unknown Date
No description available.
32

Structure-reactivity relationships in ring-slippage reactions

Fu, Yingmin January 2003 (has links)
There is no abstract available for this thesis. / Department of Chemistry
33

Transition metal promoted oxidation and reduction reactions

Gibson, Susan E. January 1984 (has links)
Two areas of organotransition metal chemistry and their potential application to organic transformations are discussed. The synthesis of cations of the type [Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(L)<sub>2</sub>(CO)]<sup>+</sup>, [Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)(L)<sub>2</sub>(CO)]<sup>+</sup>, [Fe(η<sup>5</sup>-C<sub>5</sub>(CH<sub>3</sub>)<sub>5</sub>)(L)<sub>2</sub>(CO)]<sup>+</sup> (where (L)<sub>2</sub>=(CO)<sub>2</sub>, (PPh<sub>3</sub>)(CO), (PMe<sub>3</sub>)(CO), (PPh<sub>3</sub>)<sub>2</sub>,(diphos) and (PMe<sub>3</sub>)<sub>2</sub>) and [Mo(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(L)<sub>3</sub>(CO)] (where (L)<sub>3</sub>=(PPh<sub>3</sub>)(CO)<sub>2</sub>, (diphos)(CO) and (triphos)), many of them novel, is described. Investigations into the site of nucleophilic attack on the cations using hydride as a probe and the effect of varying the overall charge distribution of the cation are discussed. Hydride attack on a carbonyl ligand leads to the formation of metal formyl moieties and their detection by low temperature <sup>1</sup>H n.m.r. spectroscopy is described; furthermore, the fate of the metal formyls was found to be dependent upon the nature of the other ligands in the complex. A new criterion for establishing the stereoselectivity of nucleophilic attack on η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub> ligands is proposed. Hydride attack on an η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub> ligand was discovered to be regioselective occurring at the carbon atom alpha to the methyl-bearing carbon. The direct oxidation of alkenes to epoxides by hydrogen peroxide was shown to be catalysed by some of the metal carbonyl cations. The use of organotitanium reagents to convert vic-dibromides and epoxides to alkenes is discussed. (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiCl<sub>2</sub> was shown to catalyse both a sodium amalgam debromination of disubstituted vic-dibromides and a zinc debromination of mono and disubstituted vic-dibromides. The latter reaction was developed into a synthetically useful procedure. Reduction of (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiCl<sub>2</sub> by both sodium amalgam and zinc dust gave reagents which deoxygenated epoxides. Investigations into the regioselectivity and chemoselectivity of these reagents are discussed. During the synthesis of molecules containing both vic-dibromide and epoxide functionalities, a novel cyclisation was discovered which may have relevance to the biosynthesis of certain marine natural products.
34

A mechanistic study of nucleophilic addition to stabilized silenes and transient disilenes /

Owens, Thomas Robert. Leigh, William J. Unknown Date (has links)
Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: William J. Leigh. Includes bibliographical references. Also available online.
35

Intramolecular ring opening reactions of aziridines by [pi]-nucleophiles /

Pulipaka, Aravinda B. January 2008 (has links)
Thesis (Ph.D.)--Ohio University, March, 2008. / Abstract only has been uploaded to OhioLINK. Includes bibliographical references (leaves 115-125)
36

Exploring reactivities of oxo and nitrido ligands on high valent osmium with electrophiles, nucleophiles, alkenes, hydrogen, and methane. /

Dehestani, Ahmad. January 2004 (has links)
Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 142-150).
37

Mechanistic Investigation of Metal Promoted Nucleophilic Additions

Arun Kumar, P January 2013 (has links) (PDF)
Nucleophilic additions are an important class of reactions in the preparation of several organic compounds. Metals facilitate nucleophilic additions in many cases. The present work Mechanistic Investigation of Metal Promoted Nucleophilic additions is an attempt to understand the mechanism of nucleophilic additions to imines and carbonyl compounds mediated by the transition metal complexes. Understanding the mechanism of metal promoted nucleophilic additions can facilitate the design and synthesis of more efficient catalysts. Chapter 1 provides a brief introduction to nucleophilic addition. A few named reactions that involve nucleophilic addition are described. An overview of the metal promoted nucleophilic addition reactions and their mechanisms are presented. A short note on the importance of understanding the mechanism of metal promoted nucleophilic addition is included. This section ends with the scope of the present work. Chapter 2 “Mechanistic Investigation of Titanium Mediated Reactions of Imines” deals with two reactions. The first reaction is the formation of reduced amines on reduction of imines. Amines and diamines are synthesized often from imines. A convenient route to such nitrogen containing compounds is through reduction of imines and through reductive coupling of imines respectively. Since both reactions occur in a parallel fashion, during the synthesis of diamines, amines are obtained as side products and vice versa. This problem is acute in the case of titanium based reducing agents. These reducing agents are called low valent titanium reagents because low valent titanium species are generated in situ either from titanium(IV) or titanium(III) reagents. There is no clear understanding of the nature of the low valent titanium involved in the reaction. To rectify this, a mechanistic understanding of this reaction is essential. An attempt was made to probe the mechanism of formation of amines using low valent titanium formed by using two different reducing agents namely phenylsilane and zinc. With the help of isotopic labelling studies, it was found that the mechanism of formation of an amine with phenylsilane involves a direct hydrogen transfer from phenylsilane to an imine. This was verified using deuterium labelled phenylsilane. With zinc, it follows a traditional titanacycle pathway which was verified by quenching with the deuterium oxide. A second reaction that has been probed is the alkylation of imines by Grignard reagents using chiral titanium complexes. Alkylation of imines is one of the suitable routes to prepare chiral amines. Alkylation of imines employing a Grignard reagent with Ti(OiPr)4 can proceed through two different pathways depending on the amount of the Grignard reagent used. Alkylation reaction with one equivalent of Grignard reagent can proceed through a Ti(IV) species and the alkylation reaction with two equivalents of the Grignard reagent can proceed through a Ti(II) species. The reaction proceeding through Ti(IV) is less wasteful as it only requires one equivalent of the Grignard reagent. The two pathways differ from each other in the nature of the transition state where the C-C bond is formed. To verify the favourable pathway, chiral titanium complexes were prepared and alkylation carried out. The alkylation results suggest that one equivalent of Grignard is sufficient to give good yields of the alkylated product and the reaction may proceed through a Ti(IV) promoted path. It was reported in the literature that at least three equivalents of Grignard reagent are required to get good yields of the alkylated product with zirconium complexes. This work suggests a greener alternate to alkylation of imines. Chapter 3 “Asymmetric Transfer Hydrogenation Reaction of Ketones in Water” deals with the synthesis of chiral ruthenium half-sandwich complexes employing a proline diamine ligand which has phenyl, ethyl, benzyl, or hydrogen as a substituent. These complexes were characterized by X-ray diffraction. In addition, all these complexes were obtained as single diastereoisomers. These complexes were used as catalysts for the reduction of a variety of ketones to chiral alcohols in water using sodium formate as a hydride source. Stoichiometric reaction between sodium formate and the catalysts showed the formation of hydride complexes as the active species. Based on the electronic effects observed, the key step is found to be a nucleophilic attack of hydride on the carbonyl carbon of ketones. In the transfer hydrogenation reaction with DCOONa, more of 1-phenylethanol- 1-2H1 was observed with all the ruthenium catalysts suggesting that the hydrogen from sodium formate is transformed into a metal hydride which is subsequently transferred to the ketones to form chiral alcohols. The catalysts were optimized with acetophenone as a model substrate. Only in the case of a catalyst which has a phenyl substituent, silver nitrate was found to enhance the formation of aqua complex which in turn resulted in good yields of the chiral alcohols. Among all the complexes studied, the catalyst bearing a phenyl group induces greatest enantioselectivity. It can also be recycled. Chapter 4 “On the Formation of a Ruthenium-PPh2H Complex Using 1- Phenylethane-1,2-diol” deals with the mechanism of formation of PPh2H from PPh2Cl. This unique transformation involves a ruthenium-cymene dimer, PPh2Cl and 1-phenylethane-1,2- diol. In the attempted synthesis of a ruthenium bisphosphinite complex, using the ruthenium-cymene dimer, chlorodiphenylphosphine and 1-phenylethane-1,2-diol, the formation of [Ru(η6-cymene)Cl2PPh2H] was observed in good yield. Formation of the expected ruthenium bisphosphinite complex was not observed. The reaction was carried out in the absence of 1-phenylethane-1,2-diol resulted in the formation of [Ru(η6- cymene)Cl2PPh2Cl] suggests that the diol acts as a reducing agent. To verify the source of hydrogen in the 1-phenylethane-1,2-diol, deuterated diols were prepared. The reactions with the deuterated diols revealed several interesting aspects of the formation of the Ru-PPh2H complex. Chapter 5 “Mechanistic Studies on the Diazo Transfer Reaction” deals with the synthesis of labelled azides and the labelled azidating reagent to probe the mechanism of the diazo transfer reaction. Azides are important precursors used for a variety of chemical transformations including the celebrated Cu(I) catalyzed click reaction. Azides are also used as protecting groups for amines as they can be conveniently reduced to amines. Azidation of amines usually yield azides, with retention of stereochemistry. There is a possibility that the azide formation can occur through the SNi mechanism with retention of configuration where nitrogen in the starting material will not be retained after forming an azide. The reaction was carried out with 13C and 15N labelled L-valine and L-isoleucine to probe this possibility. The resultant labelled azide has 15N retained in its position. This excluded the SNi pathway. To show where the nucleophilic amine group is attacking the azide, labelled imidazole-1¬sulfonyl azide was synthesized from NaN215N. Reactions were carried out with L-valine (labelled and unlabelled) in the presence of a metal catalyst and with unlabelled L-valine in the absence of catalyst. These results confirm the postulated pathways described in the literature.
38

Kinetic Studies of 6-Halopurine Nucleoside in SNAr Reactions; 6-(Azolyl, Alkylthio and Fluoro)-purine Nucleosides as Substrates for Suzuki Reactions

Liu, Jiangqiong 23 April 2007 (has links) (PDF)
In chapter 1, we describe development of a mild and efficient method for SNAr iodination of 6-chloropurine 2'-deoxynucleosides and nucleosides. Our studies demonstrate that 6-iodopurine nucleosides are excellent substrates for certain transition metal-catalyzed cross-coupling reactions. In chapter 2, we describe synthesis of protected 6-fluoro, 6-chloro, 6-bromo and 6-sulfonylpurine nucleosides. Comparisons among 6-fluoro-, 6-chloro-, 6-bromo, 6-iodo and 6-sulfonylpurine nucleosides for SNAr reactions with various N, O and S nucleophiles were investigated. Our results demonstrate that the 6-fluoropurine nucleoside is the best substrate for SNAr reactions among the four 6-halopurine nucleosides with oxygen, sulfur and aliphatic amine nucleophiles, and also with an aromatic amine plus TFA as a catalyst. However, the 6-iodopurine nucleoside is the best substrate for the aromatic amine without acid. With oxygen and sulfur nucleophiles, the 6-sulfonylpurine nucleoside reacted even faster than the 6-fluoropurine nucleoside. In chapters 3 and 4, nickel- and palladium-based systems with imidazolium-carbene ligands can catalyze efficient Suzuki cross-couplings of arylboronic acids and 6-[(imidazol-1-yl)-, (1,2,4-trizaol-4-yl), fluoro, alkylsulfanyl and alkylsulfonyl]purine 2'-deoxynucleosides and nucleosides to give the corresponding 6-arylpurine products.
39

Reaction of o-Nitrobenzenesulfonyl Azide/n-Butyl Lithium with Hindered Alcohols

Curry, Omadee S. 23 September 2013 (has links)
No description available.
40

A study of the displacement of halogen from chlorinated heteroaromatic azines by dialkali salts of benzoylacetone, disodio salts of certain 2-hydroxy-4-methylpyrimidines, and the methylsulfinyl carbanion

Greene, James Carson 25 August 2008 (has links)
Halogenated monocyclic and bicyclic heteroaromatic azines, possessing a six or ten w-electron system and one or two ring nitrogens, have been shown to undergo nucleophilic displacement of halide ion with a variety of nucleophiles. A detailed review of the relative reactivity of compounds of these classes, as well as halogenated heteroaromatic azines containing as many as four nitrogen atoms has appeared. / Ph. D.

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