New Horizons in Organic Electron Transfer
Lead Research Organisation:
University of Strathclyde
Department Name: Pure and Applied Chemistry
Abstract
Every school pupil who studies chemistry will be familiar with the reactivity of sodium metal in water. Sodium is an extremely reactive substance and readily loses an electron to become a sodium ion. Other metals also transfer electrons more or less readily.Organic molecules [containing no metals] can transfer an electron if their structures are appropriate. However, it is extremely unusual for a neutral organic molecule to be able to act as a strong electron donor. We have prepared strong electron donors and have discovered the first neutral organic molecule to be able to pass a stern test, i.e. to convert halobenzenes into aryl anions. The reactivity is unprecedented, and it gives us exciting opportunities to make further discoveries.Our aim now is to explore many aspects of the new chemistry to determine how useful it is and to push back the limits of our knowledge. As we move to more and more powerful organic electron donors, we face the tantalising prospect of creating an organic molecule equivalent in reactivity to sodium. However, our molecules would be safer than sodium and could be transported in a form that needs activation in a reaction flask.During this project we will test our molecule to see the limits of its reactivity, and we will design novel families of molecules that behave in an analogous way.
Organisations
People |
ORCID iD |
John Murphy (Principal Investigator) |
Publications
Corr MJ
(2009)
Amidine dications as superelectrophiles.
in Journal of the American Chemical Society
Corr MJ
(2009)
Amidine dications: isolation and [Fe]-hydrogenase-related hydrogenation.
in Journal of the American Chemical Society
Sword R
(2011)
Fragmentations observed in the reactions of a-methoxy-?-alkoxyalkyl iodide substrates with super-electron-donors derived from 4-DMAP and N-methylbenzimidazole.
in Organic & biomolecular chemistry
McKie R
(2007)
Homoleptic crown N-heterocyclic carbene complexes.
in Angewandte Chemie (International ed. in English)
Cutulic SP
(2009)
Metal-free reductive cleavage of C-O sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor.
in The Journal of organic chemistry
Murphy J
(2008)
Metal-Free Reductive Cleavage of N-O Bonds in Weinreb Amides by an Organic Neutral Super-Electron Donor
in Synlett
Murphy JA
(2009)
One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin.
in Journal of the American Chemical Society
Murphy J
(2008)
One-Pot Reduction of Aryl Iodides Using 4-DMAP Methiodide Salt
in Synlett
Findlay NJ
(2010)
Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand.
in Journal of the American Chemical Society
Schoenebeck F
(2007)
Reductive cleavage of sulfones and sulfonamides by a neutral organic super-electron-donor (S.E.D.) reagent.
in Journal of the American Chemical Society
Garnier J
(2010)
Structure and reactivity in neutral organic electron donors derived from 4-dimethylaminopyridine.
in Beilstein journal of organic chemistry
Murphy JA
(2008)
Super-electron donors: bis-pyridinylidene formation by base treatment of pyridinium salts.
in Organic letters
Zhou S
(2012)
The development of organic super electron donors.
in Chimia
Murphy JA
(2007)
The generation of aryl anions by double electron transfer to aryl iodides from a neutral ground-state organic super-electron donor.
in Angewandte Chemie (International ed. in English)
Description | This work led to important advances including publication of the first neutral ground-state organic electron donor (an imidazole-derived donor) that reduced iodoarenes to aryl anions (published in Angew. Chem. Int. Ed)., the reductive cleavage of activated arenesulfonamides and gem-bis-sulfones (J. Am. Chem. Soc.). It also led to a novel DMAP-derived electron donor of equal potency that did all of the above reactions as well as reduction of Weinreb amides and acyloin derivatives. This new donor |