Three-Way Chemoselectivity Switching through Coupled Equilibria in Complex System and Post-synthetic Modification of Cyclobenzoins



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Everything around us is complex systems, including ant-hills, human economies, climate systems, nervous systems, and human beings. In order to understand complex systems often requires cross-disciplinary techniques that merge the knowledge from different fields such as mathematics, physics, biology, and chemistry. In terms of system chemistry, chemists study the interaction between molecules of the systems, which exhibit a new function from a set of molecules and emerging properties. This dissertation focuses on the use of diaza-Cope rearrange as a dynamic reaction in a complex system, as well as the synthesis of the derivatives of cyclotetrabenzoin. Chapter One, selected research literature about the application of coupled equilibrium which gives the emergence properties and also multi-responsive ability, are reviewed. Chapter Two, the diaza-Cope rearrangement is used as a dynamic reaction. In coupled equilibrium between diaza-Cope rearrangement and imine exchange, three imidazolidine products can be selectively controlled based on the addition time of the oxidant. Chapter Three, thiazolium salt as an alternative catalyst was used to synthesis cyclobenzoin. The intrinsic pore of cyclobenzoin has been expanded by using various types of dialdehyde, which increase the size of the central core of cyclobenzoin. Chapter Four, the new autocatalytic cycle based on diaza-Cope rearrangement, is illustrated. However, it has not been successful yet, but it inspired the synthesis of three new macrocycles. These latest three macrocycles are based on imine condensation of cyclotetrabenzoin, which may use as gas sorption materials.



Coupled equilibrium, Cyclotetrabenzoin, Cyclobenzoin, Diaza-Cope rearrangement


Portions of this document appear in: Puangsamlee, T.; Miljanić, O. Š. Three-Way Chemoselectivity Switching through Coupled Equilibria. Org. Lett. 2020, 22, 5900–5904; and in: Eisterhold, A. M.; Puangsamlee, T.; Otterbach, S.; Bräse, S.; Weis, P.; Wang, X.; Kutonova, K. V.; Miljanić, O. Š. Expanded Cyclotetrabenzoins. Org. Lett. 2021, 23, 781–785.