Synthesis and properties of novel sequentially fluorinated motifs in organic chemistry
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
The incorporation of fluorine into organic molecules plays an increasing and major impact in all sectors of organic chemistry and the chemical industry. This is emphasised by the fact that fluorine containing compounds constitute 20% of all entities in clinical and pre-clinical trials and around 30% of agrochemical products posess a fluorine atom. Fluorinated compounds are widely represented in the materials and electronic displays sectors (polymers, liquid crystals etc). Many of these are aromatic fluorine compounds however compounds where fluorine is located at a stereogenic centre are also enjoying an increasing profile, and methods of achieving asymmetric fluorination has been a serious and widespread international objective in organic chemistry over the last decade. In this research programme we are preparaing and exploring the properties of compounds which have fluorine atoms placed adjacent to each other. The programme will explore the synthesis of compounds with three, four and six fluorine atoms arranged along a chain. These are new motifs in organic chemistry and their synthesis demands that the fluorines are introduced in a controlled and stereospecific manner, such that individual diastereoiosmers are prepared. The C-F bond has unique properties which can influence the conformation of organic molecules, and in these molecules multiple C-F bonds are placed adjacent (vicinal) to each other, and this gives rise to favoured and disfavoured conformations. The lipophilicity of these motifis will be examined and also they will be appended to functional materials such as liquid crystals, to explore their behaviour relative to known compounds. The programme will also explore the synthesis of tri-fluoro sugar analogues where three vicinal OH groups are replaced directly by three fluorine atoms. Such a replacement will help to reveal the importance of the polarity of the C-O bond versus the hydrogen bonding ability of the C-OH group in sugars, particularly as there is growing evidence that polarity is an underestimated but extremely important factor in the evolution of bio-molecules. Overall the programme will allow us to develop organo-fluorine chemistry into new territory but in a way that is relevant to a much more mainstream understanding of the behaviour and properties of organic molecules that are of commercial significance in the materials and biological chemistry sectors.
Organisations
People |
ORCID iD |
David O'Hagan (Principal Investigator) |
Publications
Hunter L
(2008)
Multi-vicinal fluoroalkanes: a new class of organofluorine compounds.
in Organic & biomolecular chemistry
Farran D
(2009)
Diastereoselective synthesis of 2,3,4,5,6-pentafluoroheptanes.
in The Journal of organic chemistry
Durie A
(2012)
The Synthesis of ?-1,2,3,4,5,6-Hexafluorocyclohexane (Benzene Hexafluoride) from Benzene
in Angewandte Chemie International Edition
Ayoup MS
(2015)
Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane.
in Beilstein journal of organic chemistry
Cormanich RA
(2015)
Particularly strong C-H···p interactions between benzene and all-cis 1,2,3,4,5,6-hexafluorocyclohexane.
in Physical chemistry chemical physics : PCCP
Bykova T
(2015)
Synthesis of selectively fluorinated cyclohexanes: The observation of phenonium rearrangements during deoxyfluorination reactions on cyclohexane rings with a vicinal phenyl substituent
in Journal of Fluorine Chemistry
Keddie NS
(2015)
All-cis 1,2,3,4,5,6-hexafluorocyclohexane is a facially polarized cyclohexane.
in Nature chemistry
Ziegler BE
(2016)
Janus Face Aspect of All-cis 1,2,3,4,5,6-Hexafluorocyclohexane Dictates Remarkable Anion and Cation Interactions In the Gas Phase.
in Journal of the American Chemical Society
Al-Maharik N
(2016)
Fluorinated liquid crystals: evaluation of selectively fluorinated facially polarised cyclohexyl motifs for liquid crystal applications.
in Organic & biomolecular chemistry
Bykova T
(2016)
Multicomponent reactions of methyl substituted all-cis tetrafluorocyclohexane aldehydes.
in Organic & biomolecular chemistry
Description | We prepared a series of selectively fluorinated aliphatics with a single fluorine on ech carbon as we progress along the carbon chain. We showed that the orientation of the C-F bonds (configuration) has a dramatic influence on the shape (conformation) of the molecule. because shape can influence properties in pharmaceuticals of liquid crystals, the the nature of the fluorination can be used as a tool to control properties. This was the overview finding. Within the project we also learned how to chemically construct these selectively fluorinated motifs. |
Exploitation Route | These findings re being taken forward to design properties into molecules relevant to liquid crystal research and agrochemicals and pharmaceuticals research. |
Sectors | Chemicals,Healthcare,Pharmaceuticals and Medical Biotechnology |
Description | EPSRC |
Amount | £388,840 (GBP) |
Funding ID | EP/HO22651/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |
Description | EPSRC |
Amount | £388,840 (GBP) |
Funding ID | EP/HO22651/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |