Synthesis of asymmetric DMAP derivatives and their applications in asymmetric catalysis and sensing

Payne, Daniel Tony (2017). Synthesis of asymmetric DMAP derivatives and their applications in asymmetric catalysis and sensing. University of Birmingham. Ph.D.

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Abstract

A library of novel chiral DMAP derivatives were synthesised from 4-chloropyridine and 3,5-dibromo-4-chloropyridine to give a diverse range of DMAP derivatives focusing on modifications at the 3-position and 3,5-positions of pyridine in DMAP. Characteristics were included in the catalyst design to allow for the formation of intramolecular cation-π interactions, which were studied with fluorescence spectroscopy. In order to achieve the desired catalyst structure, methodology was developed to allow for the facile syntheses of a diverse range of hydrocinnamaldehydes, which were subsequently used in optimised synthetic routes towards the DMAP derivatives.

The synthesised catalysts were studied in the kinetic resolution of secondary alcohols, leading to enantioenrichment of the ester and the remaining alcohol. Attempts were made to probe the pyridinium intermediate using fluorescence spectroscopy, with characteristic cation-π fluorescence responses observed when the catalysts were both alkylated and acylated.

Type of Work: Thesis (Doctorates > Ph.D.)
Award Type: Doctorates > Ph.D.
Supervisor(s):
Supervisor(s)EmailORCID
Fossey , J.S.UNSPECIFIEDUNSPECIFIED
Simpkins, N. S.UNSPECIFIEDUNSPECIFIED
Licence:
College/Faculty: Colleges (2008 onwards) > College of Engineering & Physical Sciences
School or Department: School of Chemistry
Funders: Engineering and Physical Sciences Research Council, Other
Other Funders: The Royal Society of Chemistry, Society Of Chemical Industry, The University of Birmingham
Subjects: Q Science > QD Chemistry
URI: http://etheses.bham.ac.uk/id/eprint/7459

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