Development and understanding of catalytic functionalization of amides and other organic molecules
<p>This thesis describes the development and mechanistic studies of an iridium-catalyzed reductive functionalization of amides and other catalytic transformations. The aim is to reveal and address the details of a wide variety of organic reactions, including some transition metal-catalyzed and...
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| Format: | Thesis |
| Language: | English |
| Published: |
2022
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| Summary: | <p>This thesis describes the development and mechanistic studies of an iridium-catalyzed reductive functionalization of amides and other catalytic transformations. The aim is to reveal and address the details of a wide variety of organic reactions, including some transition metal-catalyzed and organocatalytic transformations.</p>
<p>Chapter 1 introduces organic synthesis and computational chemistry and their historical backgrounds. In particular, reactions involving amines and organocatalysis are described. Chapter 2 details the development of the iridium-catalyzed reductive synthesis of azomethine ylides for [3+2] cycloaddition reactions. The unique selectivity of the cyclization reaction was extensively interrogated and explained by means of density functional theory. Chapter 3 describes mechanistic insight into the iridium-catalyzed reductive functionalization of amides. The detailed kinetic and computational studies revealed a full picture of the catalytic cycle and the high chemoselectivity in keeping with all experimental data. Chapter 4 describes computational mechanistic studies of enantioselective catalytic desymmetrization reactions of variously 4-substituted cyclohexanones. Three distinct catalytic reactions are studied, and the origin of the enantio- and diastereoselectivities for the transformations have been uncovered using density functional theory calculations. Chapter 5 describes computational mechanistic studies of enantioselective bifunctional iminophosphorane (BIMP)-catalyzed reactions. Three transformations using the BIMP catalyst are studied, and the chiral induction mechanisms originating from the stabilizing interactions are explained in detail.</p> |
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