Asymmetric Morita-Baylis-Hillmann reaction : catalyst development and mechanistic insights based on mass spectrometric back reaction screening

Isenegger, Patrick G.. Asymmetric Morita-Baylis-Hillmann reaction : catalyst development and mechanistic insights based on mass spectrometric back reaction screening. 2016, Doctoral Thesis, University of Basel, Faculty of Science.


Official URL: http://edoc.unibas.ch/diss/DissB_12002

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The aim of the research project described in chapter 2 of this thesis was to develop an efficient bifunctional phosphine catalyst that outperforms literature-known catalysts in the Morita-Baylis-Hillman reaction of methyl acrylate with aldehydes. For the evaluation of the chiral organocatalysts a mass spectrometric back reaction screening protocol of quasi-enantiomeric substrates was applied. Based on this technique, a multi-catalyst screening was developed which allowed the simultaneous determination of the intrinsic enantioselectivities of phosphines in a crude catalyst mixture. Finally, based on the data from the back reaction screening in hand together with kinetic measurements, the rate- and enantioselectivity-determining step in the catalytic cycle were identified.
In chapter 3, the synthesis of new morpholine- and piperidine-based triazolium salts and their use as NHC catalysts for the asymmetric cross-benzoin reaction is discussed. In particular, the cross-benzoin reaction between benzaldehyde and hydrocinnamaldehyde was studied. The aim of this project was to design a catalyst that could produce the desired cross-benzoin product with high enantiomeric excess and chemoselectivity.
Chapter 4 deals with the development of chiral NHC-phosphine ligands for the asymmetric iridium-catalyzed hydrogenation of different model substrates. This project was inspired by the previous work of Nanchen, a former member of the Pfaltz group. He synthesized a small library of different NHC-phosphine ligands for the hydrogenation of various substrates, however only moderate results in terms of reactivity and enantioselectivity were achieved. The aim of this project was to investigate NHC-based catalysts with conformationally more rigid structures.
Advisors:Pfaltz, Andreas and Baudoin, Olivier
Faculties and Departments:05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Synthetische organische Chemie (Pfaltz)
UniBasel Contributors:Pfaltz, Andreas and Baudoin, Olivier
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:12002
Thesis status:Complete
Number of Pages:1 Online-Ressource (371 Seiten)
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edoc DOI:
Last Modified:22 Jan 2018 15:52
Deposited On:13 Feb 2017 10:42

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