Faculty of Science School of Chemistry

Uta Wille

Lecturer

CONTACT DETAILS:

Address: Bio21 Institute, School of Chemistry, University of Melbourne, Parkville, VIC 3010 Australia

Room: Bio21 Inst., 534

Email: uwille@unimelb.edu.au

 

Teaching responsibilities

 

 

 

Field of expertise
Organic and Physical Organic Chemistry


Radicals are not only very versatile intermediates in organic synthesis but also important species involved in the damage of biological molecules. These two areas, the development of new synthetic methodologies and the study of radical-induced oxidative damage and repair of bio-relevant molecules form the basis of our current research.


Self-terminating, Oxidative Radical Cyclizations

are a novel concept in radical chemistry discovered by us recently. Upon addition of, for example, O-centred radicals XO• (where X represents inorganic or organic residues) to the C=C triple bond in alkynes, a cascade of radical transfers/cyclizations is initiated, that is terminated through homolytic scission of the O–X bond under release of an unreactive radical X• (see Scheme 1). Formally, this reaction leads to the oxidation of an alkyne to a ketone under mild conditions with the radical XO• acting as donor of O-atoms. With the help of computational methods, we are currently exploring the mechanism of this cyclization cascade in order to “design” new reactions involving main-group IV–VI-centred radicals.

 

Scheme 1



Radical Induced Oxidative Damage of Biomolecules

A close linkage between ageing and oxidative stress is indicated by the observations that reactive oxygen species generated under various conditions of oxidative stress are able to oxidize nucleic acids, proteins and lipids. Identification of the reactive intermediates and products formed during the radicalinduced oxidative damage of biological molecules is of enormous importance for the understanding of the mechanism of these reactions. This knowledge may then lead to the development novel drugs with the ability to stepping into and holding up these processes. We are interested in studying the damage (and repair?) that is caused by the atmospherically important nitrate radicals (NO3• ) on the molecules of the respiratory tract, using a combination of product, kinetic and computational methods.

 

Scheme 2

 

For further information visit the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology.

 

Selected Publications:
  1. Schiesser, C. H., Wille, U ., Matsubara, H., Ryu, I., Radicals Masquerading as Electrophiles: Dual Orbital Effects in N-Philic Acyl Radical Cyclizations and Related Addition Reactions, Acc. Chem. Res. 2007, 40, 303 - 313.
  2. Wille, U.; ANDROPOF, J., Oxidation of Aromatic Alkynes with Nitrate Radicals (NO3•): An Experimental and Computational Study on a Synthetically Highly Versatile Radical. Austral. J. Chem. 2007, 60, 420 - 428.
  3. Wille, U.; MUCKE, E.-K., Dual Orbital Effects in N-Philic Cyclizations of Silyl Radicals onto Imines, Chem. Lett. 2007, 36, 300 - 301.
  4. Wille, U., A Computational Study on the 1,2-Rearrangement in β-(Nitroxy)vinyl and β-(Acetoxy)vinyl Radicals. J. Org. Chem. 2006, 71, 4040 - 4048.
  5. Wille, U.; DREESSEN, T., Mechanistic Insights into NO3• Induced Self-Terminating Radical Oxygenations, Part I: A Computational Study on NO3• and Its Addition to Alkynes. J. Phys. Chem. A 2006, 110, 2195 - 2203.
  6. Schiesser, C. H.; Matsubara, H.; Ritsner, I.; Wille, U., Unexpected dual orbital effects in radical addition reactions involving acyl, silyl and related radicals. Chem. Commun. 2006, 1067 - 1069.
  7. Sigmund, D.; Schiesser, C. H.; Wille, U., Alkoxyl Radicals as O-Synthons in Self-Terminating Radical Oxygenations. An Experimental and Theoretical Study. Synthesis 2005, 1437 - 1444.
  8. Stademann, A.; Wille, U., NO3• Induced Self-Terminating Radical Oxygenations: Diastereoselective Synthesis of Anellated Pyrrolidines. Austral. J. Chem. 2004, 57, 1055 - 1066.
  9. Jargstorff, C.; Wille, U., Self-Terminating Radical Oxygenations: Probing the Concept by use of Various Organic O-Centered Radicals. Eur. J. Org. Chem. 2003, 3173 - 3178.
  10. Wille, U., Self-Terminating, Oxidative Radical Cyclizations: A Novel Reaction of Acyloxyl Radicals. J. Am. Chem. Soc. 2002, 124, 14 - 15.

 
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