Alkenylperoxides as in situ generated radical initiators

• Applicant: Professor Dr. Benjamin List, since 6/2020
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2017 to 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 366496560

The research project deals with alkenyl peroxides, compounds, which decompose readily into radicals at relatively low temperatures, due to their weak O-O bonds. The main goal deals with new methods for the initiation of radical chain reactions at ambient temperature or below, by generating alkenyl peroxides in situ. Various methods are known for the initiation of radical chain reactions, for example thermal and photochemical methods, as well as by redox reactions or by reaction of organometallic species with oxygen. Not all methods are equally suited for all reactions and some require special equipment or the exclusion of moisture and oxygen. The project will develop new variants of initiation by generating alkenyl peroxides in situ under specific and mild reaction conditions from relatively stable precursor compounds. These alkenyl peroxides will initiate radical chain reactions after their rapid decay into radicals. The actual initiators will thus be formed in situ by chemical induction. A second project part deals with artemisinin, a well-known natural compound, peroxide and anti-malarial, which also shows potential in cancer treatment. The mode of action of artemisinin and related peroxide-pharmaceuticals is not satisfyingly understood, but it is assumed that artemisinin forms radicals, which harm the malaria parasite in an unspecific manner. In this project, it will be investigated whether the formation of radicals can also occur via alkenyl peroxides, in addition to the generally accepted reduction by iron(II) compounds. Indications stem from preliminary experiments and the structure of artemisinin, which suggests an easy formation of alkenyl peroxides via elimination. The findings of this project could be important for the development of malaria and cancer treatment.

• DFG Programme: Research Grants
• Ehemaliger Antragsteller: Privatdozent Dr. Martin Klußmann, until 5/2020