Sustainable Radical Chemistry under Microwave Irradiation

• Applicant: Professor Dr. Armido Studer
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2003 to 2007
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5407881

Radical chemistry has meanwhile reached a very high standard in modern organic synthesis. However, many problems still remain to be solved. A big challenge is the development of environmentally benign radical reactions. This will allow the industry to use all the powerful methods offered by this interesting chemistry. In the project the application of microwave heating to perform various radical reactions is suggested. The German team in collaboration with the group of Prof. Renaud will try to expand the use of organoboron compounds as stable C-radical precursors. Hydroborations under microwave conditions will be examined as well as the extension of the radical chemistry of organoboranes for the generation alkenyl and vinyl radicals. The development of tin-free reductive cyclization processes using an extension of the cyclohexadiene chemistry developed by the German team will be investigated in Switzerland. New radical group transfer chemistry using dialkoxyboryl substituents as migrating groups will also be studied. Radical cyclizations and intermolecular additions reactions using alkoxyamines as C-radical precursors under microwave conditions will be examined. A general approach to alkoxyamines starting from boron compounds will be developed and the alkoxyamines will be used in thermal radical isomerization reactions. These processes are controlled by the so-called Persistent Radical Thermal isomerization of halides and related radical precursors under microwave heating using atom and group transfer reactions will be investigated by the Swiss group based on the results obtained by the German team for the strongly related isomerization of alkoxyamines. Reaction conditions avoiding the use of transition metal catalysts and the use of tin reagent will be examined.

• DFG Programme: Research Grants
• International Connection: Switzerland
• Participating Person: Professor Dr. Philippe Renaud