Reinvestigation of the synthetic and mechanistic aspects of manganese(III) acetate mediated reactions : synthesis of 1,2,4-trisubstituted pyrroles via amination / annulation reactions of chloroenones with chiral amine compounds

İğdir, A. Çiğdem
The first part of the thesis presents the reinvestigation of the synthetic and mechanistic aspects of manganese (III) acetate mediated reactions. The main concern about this subject was to perform a ¢- acetoxylation reactions of enones and saturated systems in shorter reactions times and higher yields than the ones known in literature reproducibly. Although successful a ¢-acetoxylation of a great variety of substrates have been reported so far, there are some problems associated with the use of Mn(OAc)3. Considering that there are not many simple methods for the direct acetoxylation of enones, optimization of Mn(OAc)3 mediated a ¢-acetoxylation of enones and reaching its maximum potential has a great importance from a synthetic and economical point of view. In the second part of the thesis, 1,2,4-trisubstituted pyrrole derivatives were the target molecules to be synthesized. Although there are quite a number of methods available for the synthesis of pyrroles, most of them involve multistep synthetic operations which lower the overall yield. There are limited reports on the preparation of the enantiomers of pyrrole derivatives having 1-N directly linked to the stereogenic center. Thus, developing a new synthetic method for the efficient preparation of polysubstituted pyrroles without racemization still remains an attractive goal.


Effects of heat treatment and chemical composition on microstructure and mechanical properties of hadfield steels
Alyaz, Serhat; Gür, Cemil Hakan; Department of Metallurgical and Materials Engineering (2003)
The aim of this thesis is to investigate the effects of Mn content and alloying additions such as Cr and Mo, and various heat treatment procedures on both microstructure and mechanical properties of austenitic manganese (Hadfield) steels. For this purpose, steels with two different Mn content were considered (12-14 Mn, 16-18 Mn). First, five different heat treatment procedures were applied to the as-cast 12-14 Mn specimens to decide the procedure resulting the optimum tensile properties. Then, the specimens...
Manganese(III) acetate based oxidation of substituted α′-position on cyclic α,β-unsaturated ketones
Tanyeli, Cihangir (2003-09-01)
Selective oxidation of the tertiary alpha'-position on various 2-cyclopentenone, 2-cyclohexenone and aromatic ketone derivatives with manganese(III) acetate is described.
Manganese(III) acetate based selective oxidation of the tertiary α′-position on various cyclic α,β-unsaturated ketones
Tanyeli, Cihangir; Iyigün, Çigdem; Elmal, Olcay (2001-09-03)
We describe the preliminary results of manganese(III) acetate based selective oxidation of various alpha ' -methyl 2-cyclohexenone and 2-cyclopentenone derivatives to afford the corresponding alpha ' -acetoxy-alpha ' -methyl substituted oxidation products in good yields. (C) 2001 Elsevier Science Ltd. All rights reserved.
Manganese (III) acetate mediated regeneration of carbonyl compounds from oximes
Altınel, Ertan; Demir, Ayhan Sıtkı; Department of Chemistry (2006)
A facile method for the direct conversion of oximes into carbonyl compounds by treatment with manganese triacetate is described. Manganese triacetate can be used for an effective and mild oxidizing agent for the regeneration of carbonyl compounds in good yield. Many functional groups are tolerated under reaction conditions.
Studies towards synthesis of urea containing helical polymers
Çalışgan, Gizem; Akdağ, Akın; Doğan, Özdemir; Department of Chemistry (2016)
This thesis deals with design and synthesis of chiral polyurea type polymers. These polymers were analyzed with molecular mechanics that they could take a helical form. The polymers are polyurea type polymers and ureas are synthesized by treating isocyanates with amines. Starting from tartaric acid, ((4S,5S)-2,2-dimethyl-1,3- dioxolane-4,5diyl)dimethaneamine was synthesized. The other diamine was naturally occuring L-lysine. These diamine functionalized compounds were treated with pphenylene diisocyanate sy...
Citation Formats
A. Ç. İğdir, “Reinvestigation of the synthetic and mechanistic aspects of manganese(III) acetate mediated reactions : synthesis of 1,2,4-trisubstituted pyrroles via amination / annulation reactions of chloroenones with chiral amine compounds,” Ph.D. - Doctoral Program, Middle East Technical University, 2006.