Computational and mechanistic studies on the formation of cyclic systems /

2017
Sarı, Özlem
Nowadays, computational chemistry has become an important tool in life sciences especially in organic chemistry. Development of various computational techniques let us to understand the nature of the organic molecules, elucidate the reaction mechanisms and design new catalysts. Computational chemistry can also provide valuable molecular insights into the geometrical and electronic properties of molecules. This study presents a combined experimental and computational analysis of various reactions and transformations; such as intramolecular cyclization, hydroamination, bromination, propargyl-allene isomerization, epoxidation and asymmetric allylic arylation. In the first part of the study, density functional theory calculations were carried out to assess the mechanism of the formation of pyrrolotrizaepine and pyrrolotrizaepinone derivatives. In the second part, the reaction of N-propargyl carbaldeyde with different types of amines such as primary amines, alkyl amines and bulky amines were evaluated. In the next part, experimentally observed regioselectivities and stereoselectivities of bromination and epoxidation reactions were examined by means of theoretical calculations. After that, intramolecular cyclization reaction of O-propargylated pyrazole derivatives for the construction of benzopyrazoloxazepines and benzopyrazoloxasocines were studied with density functional theory calculations. In the final part of the study, enantioselectivity observed in the rhodium catalyzed asymmetric allylic arylation reaction was theoretically investigated. 
Citation Formats
Ö. Sarı, “Computational and mechanistic studies on the formation of cyclic systems /,” Ph.D. - Doctoral Program, Middle East Technical University, 2017.