Alkenes as Nucleophiles in Catalytic Asymmetric C-C Bond Formation
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
This program aims to develop methods to use simple, readily available starting materials to build up more complex organic chemicals. The chemicals we are aiming to make have the property of being 'one handed' (for example, left handed), where the normal course of events in chemistry is to produce a 50:50 mixture of right and left handed molecules. Methods to produce one handed molecules already exist but are often impractical because they rely on using starting materials that contain metals (highly reactive and sensitive to temperature, air and water). Being able to use alkenes, which are readily available, rather than metal containing chemicals would simplify a number of very useful processes in chemistry and industry. This will allow certain valuable reactions to be done much more quickly and efficiently while minimizing waste and improve the process in a very 'green' way.
People |
ORCID iD |
| Stephen Fletcher (Principal Investigator) |
Publications
Anger E
(2015)
Simple Azo Dyes Provide Access to Versatile Chiroptical Switches
in European Journal of Organic Chemistry
Bassolino G
(2014)
Synthetic control of retinal photochemistry and photophysics in solution.
in Journal of the American Chemical Society
Bissette AJ
(2014)
Physical autocatalysis driven by a bond-forming thiol-ene reaction.
in Nature communications
Bissette AJ
(2015)
Systems chemistry: Selecting complex behaviour.
in Nature chemistry
Bissette AJ
(2013)
Mechanisms of autocatalysis.
in Angewandte Chemie (International ed. in English)
Bissette AJ
(2015)
Novel applications of physical autocatalysis.
in Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life
Caprioglio D
(2015)
An alternative synthesis of the breast cancer drug fulvestrant (Faslodex®): catalyst control over C-C bond formation.
in Chemical communications (Cambridge, England)
Castellanos A
(2011)
Current methods for asymmetric halogenation of olefins.
in Chemistry (Weinheim an der Bergstrasse, Germany)
| Description | We have developed new asymmetric C-C bond forming reactions that use alkenes as non-stabilised nucleophile equivalents. |
| Exploitation Route | The new methods are likely to be useful in the preparation of new materials, medicinal chemistry, structure determination, and the synthesis of drugs. |
| Sectors | Chemicals |
| Description | ERC Consolidator Grant |
| Amount | € 2,278,073 (EUR) |
| Organisation | European Research Council (ERC) |
| Sector | Public |
| Country | Belgium |
| Start | 06/2016 |
| End | 05/2021 |
| Description | Understanding what molecular factors control photochemistry |
| Organisation | University of Oxford |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | Design and synthesis of chromophores. Measurement of quantum yield |
| Collaborator Contribution | Measurement of photo physics, design of chromophores. |
| Impact | 2 publications in Journal of the American Chemical Society on retinal photochemistry. |
| Start Year | 2010 |
| Description | light in control of the helix |
| Organisation | University of Twente |
| Country | Netherlands |
| Sector | Academic/University |
| PI Contribution | Design and synthesis of molecular switches |
| Collaborator Contribution | fabrication of helical polymers, study of properties |
| Impact | Recently funded EPSRC grant to research how to convert molecular movement to the macro scale. We received a Royal Society Travel Grant. |
| Start Year | 2011 |
| Title | ASYMMETRIC SYNTHESIS OF CHIRAL COMPOUNDS |
| Description | The present invention provides processes for the production of chiral compounds in a stereoisomeric excess, the processes comprising: (i) contacting a first compound comprising an alkene or alkyne bond with a hydrometallating agent, wherein the first compound and the hydrometallating agent are contacted under conditions such that the first compound is hydrometallated by said hydrometallating agent; and (ii) contacting the hydrometallated first compound with a second compound comprising an allylic group, wherein the hydrometallated first compound and the second compound are contacted under conditions such that they undergo an asymmetric allylic alkylation reaction in which a carbon atom of the hydrometallated first compound binds to a carbon atom of said allylic group, forming a stereoisomeric excess of a compound having a chiral centre in an allylic position, said chiral centre being located at the carbon atom bound by said first compound, wherein said asymmetric allylic alkylation reaction is performed in the presence of a metal catalyst comprising a chiral ligand. In particular, the present invention provides processes for the production of a stereoisomeric excess of a compound of the formula (IA), (IB), (IA') or (IB') as defined herein. |
| IP Reference | WO2015008097 |
| Protection | Patent application published |
| Year Protection Granted | 2015 |
| Licensed | No |
| Impact | n/a |
| Title | ASYMMETRIC SYNTHESIS OF ORGANIC COMPOUNDS |
| Description | The present invention provides processes for the production of chiral compounds in a stereoisomeric excess. The present processes involve reacting a hydrometallated alkene compound with a compound comprising a conjugated -bond system under conditions such that the compounds undergo an asymmetric 1,4- or 1,6-conjugate addition reaction, generating a chiral compound in a stereoisomeric excess. The reaction is performed in the presence of a metal catalyst, which catalyst preferably comprises a non-racemic chiral ligand. |
| IP Reference | WO2013054131 |
| Protection | Patent application published |
| Year Protection Granted | 2013 |
| Licensed | No |
| Impact | Sigma Aldrich now sells a catalyst complex that was invented during this work |
| Title | CATALYSTS, LIGANDS AND USE THEREOF |
| Description | According to the present invention, there is provided a catalytic complex comprising a metal, one or more ligands and one or more counterions, wherein said one or more ligands include a non-racemic chiral ligand and wherein said one or more counterions include a triflimide counterion. Also provided are methods of making said catalytic complex and processes for producing chiral compounds which involve the use of said catalytic complex. In addition, the present invention provides compounds of the formula (2) as defined herein. The compounds of formula (2) may be useful as ligands in catalytic complexes. |
| IP Reference | WO2014170642 |
| Protection | Patent application published |
| Year Protection Granted | 2014 |
| Licensed | No |
| Impact | We developed a new series of chiral non-racemic ligands for use in asymmetric catalysis which should find widespread use in the near future. |