Controlling selectivity by crystal engineering on aldolization and cycloaddition in the solid-state
(2024)
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- Authors
- Supervisors
- Leyssens, Tom
- Abstract
- This thesis explores the intersection between asymmetric organic synthesis and crystal engineering, positioning itself in the field of green chemistry through its low solvent usage. It focuses on the use of cocrystals to control the selectivity of organic reactions, such as asymmetric solid-phase aldolization reactions and photochemical cycloadditions [2+2]. The influence of the specific solid form of the catalyst on the stereochemical selectivity of the products in an asymmetric aldolization reaction was clearly shown. The use of a mixture of D- and L-proline cocrystallized with fumaric acid as catalyst enabled a higher enantiomeric excess to be achieved than with its non-cocrystallized form. Research has also explored solid-phase photodimerization of cinnamic acids, where the specificity of the reaction is dictated by the crystal structure of the reactants. By cocrystallizing cinnamic acid molecules, it has been possible to control the orientation of the molecules within the crystal structure where the photoaddition occurs, favoring the production of specific regioisomers. In particular, this approach enabled the controlled synthesis of β-truxinic acid. At this stage, the developed tools lack in predictability to be used as such for organic synthesis. Nonetheless, this thesis shows that the packing of organic molecules governed by weak interactions can influence the outcome of organic reactions and controlling this packing by the means of crystal engineering could eventually join the organic chemist’s toolbox.
- Affiliations
Citations
Body, C. (2024). Controlling selectivity by crystal engineering on aldolization and cycloaddition in the solid-state. https://hdl.handle.net/2078.5/215302