Enols and Allylic Alcohols as Building Blocks in Synthetic Organic Chemistry : Experimental and Theoretical Studies

Abstract: The present thesis describes computational and experimental studies used to drive the reactivity of allylic and enol substrates towards new transformations. These synthetic methods give access to a number of organic molecules that may serve as important moieties in synthetic organic chemistry. Additionally, this thesis describes the synthesis of Metal-Organic Frameworks (MOFs) and their use in catalytic organic reactions. The introductory chapter (Chapter 1) gives an overview of the concept of catalysis and its typologies, emphasizing those that have been used in the thesis. Moreover, synthetic procedures for the formation of MOFs and their use in catalysis are described. The importance and reactivity of allylic substrates are also presented. The chapter follows with a short introduction to hypervalent iodine and their reactivity. Finally, a brief description of computational studies and those used in this thesis are presented. In Chapter 2, an umpolung protocol for the cross-nucleophile coupling of silyl enol ethers with heteronucleophiles mediated by an hypervalent iodine reagent has been explored (Paper I). The mechanistic study of the reaction has been carried out employing DFT calculations and kinetic investigations. Together with deuterium labelling studies and kinetic simulations, DFT calculations have been used in Chapter 3 for the examination of the base-catalyzed [1,n]-proton shift in conjugated polyenyl ethers (Paper II). Chapter 4 describes the synthesis of the family MIL-101(Cr) and MIL-101(Cr)-NH2 employing microwave-assisted methods. The method has been compared to the common solvothermal synthetic pathways using common characterization techniques for heterogeneous materials (Paper III). Finally, Chapter 5 of this thesis describes the synthesis of a UiO-67 MOF containing a phosphazene superbase to study the effect of spatial confinement within a MOF on the stereospecific isomerization of allylic alcohols (Paper IV).