Applications of density functional theory (DFT) in organic and inorganic reactions

A Gouranourimi
2020
The first chapter provides a brief introduction to the computational methods used in this thesis. The second and third chapters of this thesis, "Amino-Cope Rearrangement and its anionic form: a mechanistic study from the DFT perspective" and " Development of a Novel Application of the Amino-Cope Rearrangement", outline the development of an original, unified synthetic strategy that will provide conspicuous and distinctive access to a range of structurally diverse lycopodium, cylindricine, and
more » ... cylindricine, and lepadiformine alkaloids and their derivatives. Specifically, this is achieved by establishing an unprecedented method for the efficient preparation of annulated medium-size N-heterocycles via the novel application of an anionic Amino-Cope Rearrangement (ACR). In addition to identifying and defining new synthetic strategies, the results in these chapters will improve the ability to construct complex biologically significant compounds, enhance fundamental understanding of organic molecules and explore key principles of chemical reactivity and mechanism. The Amino-Cope Rearrangement and its anionic form have been investigated mechanistically and experimentally in these chapters. Progress in synthesis is a few steps away from making the Amino-Cope Rearrangement substrate required to provide the product after the rearrangement. From a mechanistic point of view, different kinds of this rearrangement were explored: Neutral ACR, metallated ACR, and naked ACR, finding that while the neutral ACR proceeds via a concerted pathway, metallated and naked ACR goes through the step-wise mechanism. With the information from the DFT results, it is anticipated that the rearrangement on the substrate will be able to be performed in the future in order to investigate this area more deeply. In the fourth and fifth chapters of this thesis, an important organic reaction called Nazarov cyclization is explored. In the fourth chapter, DFT has been utilised to study the mechanism of Nazarov cyclisations initiated by oxidation of pentadienyl ethers b [...]
doi:10.25959/100.00034914 fatcat:x2zd7z4w2jeutityoqk4d6ropy