<p><font face="TimesNewRomanPSMT"> <p align="left">This thesis reports the synthesis of the imine ligands from Schiff base condensation reaction of aldehyde derivatives and equimolar quantities of aniline derivatives. The imine ligands spectrometry.</p> </font></p>

<p><font face="TimesNewRomanPSMT"> <p align="left">This thesis reports the synthesis of the imine ligands from Schiff base condensation reaction of aldehyde derivatives and equimolar quantities of aniline derivatives. The imine ligands spectrometry.</p> </font></p>

Magister Scientiae - MSc / This thesis reports the synthesis of the imine ligands from Schiff base condensation reaction of aldehyde derivatives and equimolar quantities of aniline derivatives. The imine ligands spectrometry.

Developing asymmetric C-H bond activation methods in order to achieve enantiopure products is crucial for the advancement of the field and for the production of novel chiral compounds. Therefore, we tried to develop this area of organic chemistry by presenting metal catalyzed stereoselective C-H bond activation utilizing chelation-assisted tools. The first section of this study involves Rh(I) catalyzed asymmetric C-H bond activation of a series of ketones via an intermolecular procedure. By this method, we examine ortho-alkylation of aromatic ketones and β-functionalization of α-β unsaturated ketones with a series of prochiral olefins. In the second section, we present an efficient three steps method for stereoselective intramolecular C-H bond activation of indol-3-carboxaldehyde with tethered prochiral olefins. The catalytic system in both methods involves a joint chiral primary amine and Rh(I) catalyst. Chiral primary amines can serve to induce enantioselectivity as well as acting as a useful directing group which has shown appropriate coordination to the transition metal catalyst, providing high regioselectivity. / February 2017

An effiecient stoichiometric amount system has been developed for the synthesis of N-phenylpyridin-2-amine Palladacycle, and then reation with aryl trifluoroborate to 9-(pyridine-2-yl)-9H-carbazoles by C-H bond activation/ C-C bond formation and C-N bond formation. The subsitutent effect of the aryl trifluoroborate with N-phenylpyridin-2-amine Palladacycle intermediate was observed. Mechanistic studies of C-H bond cleavaged, including trapping of reaction intermediates and kinetic isotope effect experiments, are also presented.

The work described in this thesis documents the development of new rhodium(I)-catalysed methodologies within two areas of research. The first examines the use of carbonyls as chelating groups in hydroacylation to produce synthetically valuable ketones and enones. The second area explores new carbon-carbon bond activation methodologies. Chapter 1 presents a literature review of the historical development of rhodium-catalysed hydroacylation, with a focus on chelating groups that can currently be used to suppress decarbonylation. A brief review of methodologies that avoid the requirement for a tether is also included. Chapter 2 describes the development of a novel hydroacylation methodology employing carbonyl-based functional groups as tethers on aldehyde substrates. The chapter begins with the optimisation studies for the hydroacylation of &beta;-formyl amides with terminal and internal alkynes, allenes and terminal alkenes, and subsequently explores the substrate scope for each case. The chapter then outlines the investigations undertaken with 1,4-dicarbonyl and 1,5-dicarbonyl systems, N-formyl amides, &beta;-formyl esters and finally &beta;-formyl ketones. A detailed description of the routes undertaken to synthesise each starting material is also presented. Chapter 3 presents a short review surveying the key milestones in the development of carbon-carbon activation methodologies. The chapter begins with a theoretical comparison to carbon-hydrogen activation and a discussion of the unique challenges that are faced. An overview of the major strategies employed to enact these processes is subsequently presented for both strained and unstrained substrates. Chapter 4 outlines the attempts undertaken to develop a novel carbon-carbon bond activation methodology. The work evaluates sulfur-, nitrogen- and alkene-based chelating groups, known to be successful in hydroacylation, in analogous ketone substrates. Chapter 5 discusses the conclusions from this work and the potential for further work. Chapter 6 presents the experimental procedures and data.

No description available.

N-phenylpyridin-2-amine , treated with stochiometric amount of palladium(II) acetate in dichloromethane at 65-70¢J for 4 h, to give high yield palladacycle 53. The reaction of palladacycle 53 with potassium aryltrifluoroborates in 1,4-dioxane at 140¢J for 24 h, could give a variety of N-(2-pyridinyl)carbazoles 55a-55m via sequential C-H bond activation. Carbazole derivative 55a reacted with irdium chloride gave iridium dimer, which followed by addition of picolinic acid via ligand exchange will form iridium complexes, which can further be utilized as OLEDs materials.

This thesis is composed of two parts. The palladium-catalysted synthesis of 2-arylphenols and carbazoles via carbon-hydrogen (C-H) bond activation is described. Treatment of 2-phenoxypyridines with two and a half equivalents of potassium aryltrifluoroborate and 10 mol % of Pd(OAc)2 in the presence of two equivalents of Ag2CO3, one equivalent of p-benzoquinone (BQ), and four equivalents of DMSO with (or without) H2O at 130-140 oC for 48 h in dried CH2Cl2 gave the ortho-arylated 2-phenoxypyridines in modest to excellent yields. The investigation of kinetic isotope effect (kH/kD) is determined to be 5.25, which indicates that C-H bond cleavage occurs in the rate-determining step. 2-(Biphenyl-2-yloxy)pyridines was treated with methyl trifluoromethanesulfonate and subsequently sodium methoxide to give the 2-arylphenols to demonstrate the pyridine is a removable directing group. On the other hand, a novel one-pot synthesis for N-pyridylcarbazoles by the reaction of N-phenylpyridin-2-amines with potassium aryltrifluoroborates using Pd(OAc)2 as the catalyst is presented. For instance, reaction of N-phenylpyridin-2-amines with four equivalents of potassium aryltrifluoroborate under the optimal reaction condition gave N-pyridylcarbazoles in 67% yield along with N-(biphenyl-2-yl)pyridin-2-amine in 13% yield. The investigation of kinetic isotope effect (kH/kD) for first C-H bond activation/C-C bond formation step is determined to be 2.14, and that of the second C-H bond activation/C-N bond formation steps is 1.18. On the basis of KIE analysis, it might indicate that first C-H activation undergo direct C-H bond cleacage, and second step should be via electrophilic aromatic substitution.

A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation, in which palladium(II)-catalyzed cross-coupling of 9-(pyridin-2-yl)-9H-carbazoles with potassium aryltrifluoroborates is presented. Silver nitrate and tert-butanol were proved to be the best oxidant and solvent for the process, respectively. The product yields fluctuated from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, 9-(pyridin-2-yl)-9H-carbazole palladacycle was isolated and confirmed by X-ray crystallography. The kinetic isotope effect (kH/kD) for the C-H bond activation step was measured as 0.87. In addition, Hammett experiment gave a negative rho value, -2.14 with a reasonable correlation (R2 = 0.90). The directing group, pyridyl was demonstrated as a removable functional group. Finally, a rational catalytic mechanism is presented based on all experimental evidence.