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Visible light assisted introduction of fluorinated building blocks to amine scaffolds via cross-dehydrogenative couplings

Visible light assisted introduction of fluorinated building blocks to amine scaffolds via cross-dehydrogenative couplings
Visible light assisted introduction of fluorinated building blocks to amine scaffolds via cross-dehydrogenative couplings
From the beginning, when synthetic chemistry began there has always been an endeavour to discover and create new organic methodologies in chemistry. However, as we come into the 21st century and our understanding of what’s possible in chemistry increases so does the realisation that the resources available are rapidly depleting. As such we have chosen to undertake and present the merging of “green” and new photocatalytic methodologies.

The opening chapter describes the preliminary investigation into the use of a photocatalysed cross-dehydrogenative coupling reaction to introduce nucleophilic fluorinated building blocks into the C1 position of an N-aryltetrahydroisoquinoline. To this extent, an effective method to introduce the dimethylfluoromalonate group has been reported with a high tolerance to electron neutral and electron withdrawing moiety’s obtaining good to high yields, and strongly electron donating groups achieving moderate yields.

In the second chapter, an investigation into introducing selectivity into fluorinated cross-dehydrogenative couplings. The reaction envisaged the use of an organocatalyst to introduce enantioselectivity in the reaction between 1-fluoroacetone and N-aryl tetrahydroisoquinoline. The reaction proceeded with good to excellent yields with a variety aryl groups. The use of a primary cyclohexane diamine catalyst resulted in a promising enantioselectivity, demonstrating that an environmentally friendly methodology can induce selectivity.

In the final chapter, an elegant methodology for the addition and subsequent desulfonylation of the 1-fluoronitrophenylsulfonyl methane. Both transformations are completed by the use of visible light in conjunction photosensitizer. The reaction proceeds with good to excellent yields, and moderate diastereoselectivities tolerating a variety of electronic effects on the tetrahydroisoquinolines.
University of Southampton
Shirley, Luke
18fb5c30-94b6-40f7-8db4-1db1ea1b0126
Shirley, Luke
18fb5c30-94b6-40f7-8db4-1db1ea1b0126
Rios Torres, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441

Shirley, Luke (2017) Visible light assisted introduction of fluorinated building blocks to amine scaffolds via cross-dehydrogenative couplings. University of Southampton, Doctoral Thesis, 179pp.

Record type: Thesis (Doctoral)

Abstract

From the beginning, when synthetic chemistry began there has always been an endeavour to discover and create new organic methodologies in chemistry. However, as we come into the 21st century and our understanding of what’s possible in chemistry increases so does the realisation that the resources available are rapidly depleting. As such we have chosen to undertake and present the merging of “green” and new photocatalytic methodologies.

The opening chapter describes the preliminary investigation into the use of a photocatalysed cross-dehydrogenative coupling reaction to introduce nucleophilic fluorinated building blocks into the C1 position of an N-aryltetrahydroisoquinoline. To this extent, an effective method to introduce the dimethylfluoromalonate group has been reported with a high tolerance to electron neutral and electron withdrawing moiety’s obtaining good to high yields, and strongly electron donating groups achieving moderate yields.

In the second chapter, an investigation into introducing selectivity into fluorinated cross-dehydrogenative couplings. The reaction envisaged the use of an organocatalyst to introduce enantioselectivity in the reaction between 1-fluoroacetone and N-aryl tetrahydroisoquinoline. The reaction proceeded with good to excellent yields with a variety aryl groups. The use of a primary cyclohexane diamine catalyst resulted in a promising enantioselectivity, demonstrating that an environmentally friendly methodology can induce selectivity.

In the final chapter, an elegant methodology for the addition and subsequent desulfonylation of the 1-fluoronitrophenylsulfonyl methane. Both transformations are completed by the use of visible light in conjunction photosensitizer. The reaction proceeds with good to excellent yields, and moderate diastereoselectivities tolerating a variety of electronic effects on the tetrahydroisoquinolines.

Text
Luke Shirley thesis - 27408175 - Version of Record
Restricted to Repository staff only until 28 June 2021.
Available under License University of Southampton Thesis Licence.

More information

Published date: November 2017

Identifiers

Local EPrints ID: 422227
URI: http://eprints.soton.ac.uk/id/eprint/422227
PURE UUID: b99650b0-26da-4693-934d-ac6b744dae6a
ORCID for Ramon Rios Torres: ORCID iD orcid.org/0000-0002-3843-8521

Catalogue record

Date deposited: 19 Jul 2018 16:30
Last modified: 14 Mar 2019 01:35

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Contributors

Author: Luke Shirley
Thesis advisor: Ramon Rios Torres ORCID iD

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