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

Abstract

The presen thesis describes computational and experimental studies used to drive the reactivity o allylic and enol subtrates 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 gives an overview of the concept of catalysis emphasizing those that have been used in the thesis. Moreover, synthetic procedures for the formation of MOFs and their use in catalysis. The importance and reactivity of allylic substrates are also presented. A short introduction to hypervalent iodine and their reactivity. Finally, a brief description of computational studies. Chapter 2, an umpolung protocol for the cross-nucleophile coupling of silyl enol ethers with heteronucleophiles mediated by a benzodioxole. The mechanistic study of the reaction has been carried out employing DFT calculations and kinetic investigations. Paper ITotgether 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 IIChapter 4, describes the synthesis of the family MIL-101(Cr) and MIL-101-NH2(Cr) employing microwave-assisted methods. The method has been compared to the common solvothermal synthetic pathways using common characterization techniques for heterogeneous materials. Paper IIIFinally, Chapter 5 of this thesis describes the synthesis of a UiO-67 MOF containing a iminophosphorane superbase to study the effect of spatial confinement within a MOF on the stereospecific isomerization of allylic systems. Paper IV, Supporting Information.