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Development of sustainable catalytic methods
Boek - Dissertatie
Ondertitel:aza-cope rearrangement of homoallylamines and thiosulfonylation of alkenes
A major issue within chemistry is the use of expensive, non-renewable and toxic reagents/reactants, catalysts or solvents to carry out organic reactions. The replacement of these by inexpensive, abundant and benign alternatives is an ongoing challenge for the chemical community. The research of this doctoral thesis is focused on the development of novel sustainable methodologies for the synthesis of α-substituted homoallylamines via 2-aza-Cope rearrangement and subsequent functionalization of its alkene moiety via visible light photocatalysis. α-Substituted homoallylamines are valuable synthetic building blocks and precursors for the synthesis of a variety of nitrogen containing heterocycles, natural products and pharmaceutical compounds in organic synthesis and medicinal chemistry. In this doctoral thesis, a metal-free or base-metal-catalyzed 2-aza-Cope rearrangement strategy has been developed for the synthesis of α-substituted homoallylamines by using easily accessible aldehydes and 1,1-diphenylhomoallylamines. Alkenes are one of the most fundamental functional groups in organic chemistry and are often derived from simple chemical feedstock. In the past few decades, the functionalization of alkenes has caught tremendous attention, especially strategies to achieve functionalization in an anti-Markovnikov manner were the focus of fundamental research. The installation of sulfonyl (R1SO2-) and sulfenyl (R2S−) moieties specifically is of application interest as they appear in natural products, bioactive molecules, and pharmaceuticals. Besides, they are attractive functionalities in organic synthesis as they are easily transformed into other functional groups. Direct functionalization methods of alkenes, which allow to introduce two different groups in a single reaction step such as the thiosulfonylation are therefore highly desired. In this doctoral thesis, a metal-free methodology for the vicinal thiosulfonylation of unactivated alkenes has been developed by using thiosulfonates as a reactant and the acridinium salt 9-mesityl-10-methylacridinium perchlorate as a photo-organocatalyst with visible-light irradiation. To illustrate the synthetic potential, the method was applied for homoallylamines and late stage functionalization of olefins in active pharmaceutical ingredients.
Aantal pagina's: 331
Jaar van publicatie:2022