- Direct activation of allylic alcohols in palladium catalyzed coupling reactions
- Award date
- 21 October 2014
- Number of pages
- Document type
- PhD thesis
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to develop new methods to activate (bio-mass derived) allyl-alcohols, which allow ‘green’ chemical processes for a broad substrate range. This may have a considerable impact on the methodology for fine chemical transformations in the pharmaceutical and fragrance industries. With the work described in this thesis, we aim to develop a novel waste-free catalytic system for the direct substitution reactions of allylic alcohols in alkylation and amination reactions yielding water as the only ‘waste product’. For this purpose a phosphoramidite based palladium catalyst, 1, operating in a supramolecular fashion by an additional 1,3-diethylurea moiety as the cocatalyst was developed. In the light of biomass utilization, we have explored the compatibility of this system with terpenols to get easy access to a variety of biologically active and fine chemical industry related products. To get a better understanding of the system and to facilitate future developments, mechanistic studies were performed (detailed kinetic analysis and DFT calculations).
- Research conducted at: Universiteit van Amsterdam
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