Reversible Covalent and Noncovalent Interactions in Organoboron Catalysis and Solution Phase Chalcogen Bonding

The covalent and noncovalent interactions that occur between molecules are at the heart of a wealth of chemical applications. This work describes studies of these interactions in the design of new compounds for molecular sensing and recognition (Chapters 1â 3), and catalysis (Chapters 3 and 4). In Chapter 1, a systematic study on telluradiazole chalcogen bonding interactions delineates the thermodynamic driving forces behind the formation of these noncovalent bonds. This information was applied in Chapter 2 in the design of a bidentate tellurophene capable of solution phase anion recognition. In Chapter 3, the covalent interactions between a new class of b-aminoalkylboronic acids and carbohydrates were explored. Additionally, the b-aminoalkylboronic acids were found to be catalytically active in regioselective diol acylation reactions. This work suggests that b-aminoalkylboronic acids are a promising candidate for future catalyst and carbohydrate sensor development. In Chapter 4, a mechanistic study on the diphenylboronic acid catalyzed chloroacylation of 2,3-epoxy alcohols is presented which reveals the catalystâ s unusual role at activating the substrate as both an electrophile and as a nucleophile. Future directions for improving the scope of the reaction to include new nucleophiles and electrophiles are suggested based on the mechanistic results. In Chapter 5, a new method for creating graphical rate equations from integral data is presented. The method uses curve fitting to a first order nonlinear ordinary differential equation. This method is shown to be applicable to a range of reactions with diverse mechanistic behaviour. Additionally, the graphical rate equations created from this method are shown to be insensitive to the size, noise level, and experimental duration of the data set. The method also provides a means to accurately define areas of statistical similarity, or overlay, during reaction progress kinetic analysis.Ph.D