Studies towards the Organocatalytic ‘Dialled In’ Synthesis of Chiral, Non-Racemic Aziridines, and Amino Acids, Containing Multiple Isotopic Labels

Thurston, Sean (2012) Studies towards the Organocatalytic ‘Dialled In’ Synthesis of Chiral, Non-Racemic Aziridines, and Amino Acids, Containing Multiple Isotopic Labels. Doctoral thesis, University of East Anglia.

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Abstract

Within this thesis, a highly effective one-pot methodology (based around the use of
the organocatalyst pyridinium triflate) has been developed for the highly cis-selective
synthesis of N-aryl 3-aryl-aziridine-2-carboxylates as racemates in yields of up to 80 %.
This methodology has been extended by the use of a highly acidic C2 symmetric 3,3’-
anthracenyl functionalised BINOL triflylphosphoramide organocatalyst, which allows for
the formation of the desired cis- N-aryl 3-aryl-aziridine-2-carboxylates in an effective and
highly enantioselective manner (affording the desired materials in yields of up to 81 %,
and e.e.s of >99 %).
Utilising the methodology developed within the first part of the thesis, enantio- and
isotopically enriched cis- N-aryl 3-aryl-aziridine-2-carboxylates have been synthesised in a
regioselective manner; with deuterium selectively introduced at the C2, and/or C3
positions of the aziridine ring with generally >90 % isotopic enrichment. Further to this,
these aziridines have been submitted to ring opening methodologies in order to produce
enantiomerically enriched a-amino acid derivatives bearing regioselectively introduced
deuterium labels (with generally >90 % isotopic enrichment), in yields of up to 97 %, and
e.e.s of up to 97 %,
Finally, these methods have been combined in order to synthesise 5 target
molecules consisting of functionalised enantioenriched a-amino acid derivatives bearing
multiple isotopic labels including deuterium, 15N, and 18O, in what has become known as
the ‘Dialled In’ methodology.

Item Type: Thesis (Doctoral)
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Mia Reeves
Date Deposited: 16 May 2013 15:44
Last Modified: 16 May 2013 15:44
URI: https://ueaeprints.uea.ac.uk/id/eprint/42423
DOI:

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