Kinetic resolution strategies

Thesis



This thesis is concerned with the use of kinetic resolution strategies for the preparation of enantiomerically pure materials.

Chapter 1 introduces kinetic resolution. The limitations of conventional kinetic resolutions are described and the methods used to overcome these limitations are discussed.

Chapter 2 presents a double kinetic resolution strategy where the recovered reactant from the first kinetic resolution is used as starting material in a second kinetic resolution. In the second kinetic resolution the major enantiomer present in the starting material is the faster reacting enantiomer. Application of this double kinetic resolution strategy to the Sharpless epoxidation is shown to enable enhanced product enantiomeric excesses to be obtained.

Chapter 3 presents an alternative double kinetic resolution strategy where the product from the first kinetic resolution is used as starting material in a second kinetic resolution. In the second kinetic resolution the major enantiomer present in the starting material is the faster reacting enantiomer. Application of this double kinetic resolution strategy using lipase mediated esterification and hydrolysis reactions is shown to enable enhanced product yields to be obtained.

Chapter 4 describes the preparation of an enantiomerically pure 2-substituted monoprotected propan-1,3-diol derivative via combination of an asymmetric synthesis and a kinetic resolution.

Chapter 5 describes the preparation of the pheromone sulcatol in enantiomerically pure form via combination of an asymmetric synthesis and a kinetic resolution.

Chapter 6 presents an investigation into the structure of lithium(α-methylbenzyl)- benzyl amide.

Chapter 7 describes an attempted dynamic kinetic resolution of 2-substituted monoprotected propan-1,3-diol derivatives.

Chapter 8 describes an attempted preparation of the iron crotonyl complex E-[(η⁵-C₅H₅)Fe(CO)(PPh₃)(COCH=CHCH₃)] in enantiomerically pure form via enzymic kinetic resolution.

Authors: De Sousa, J; J A A de Sousa

• Publication date: 1992
• DOI: 10.5287/ora-qzogjkekn
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Subjects: Separation; Chirality; Amino acids; Synthesis; Diastereoisomers; Esters