Skip to main content
Go to the home page of the European Commission (opens in new window)
English en
CORDIS - EU research results
CORDIS

Development of a boryl radical-mediated H-atom transfer umpolung blueprint to make nucleophilic radicals behave as electrophilic species

Project description

New paths in radical chemistry

Aliphatic molecules are essential in many chemical processes, but creating them can be difficult due to the behaviour of alkyl radicals. These radicals are typically nucleophilic, meaning they do not react well with electron-rich compounds such as aromatics and olefins. On the other hand, electrophilic radicals do react strongly with these compounds, but are not widely useful in synthetic chemistry. Supported by the Marie Skłodowska-Curie Actions programme, the BRAT project will develop a new method to reverse the behaviour of these radicals. By combining photoredox catalysis with boryl radical-mediated H-atom transfer, the project will generate new radicals that can react with electron-rich compounds. This will facilitate the creation of high-value aliphatic products and expand the possibilities of radical chemistry.

Objective

"Aliphatic molecules are integral to every aspect of chemistry and radical chemistry has strong impact in their preparation. However, radical reactions are heavily influenced by the polarity of these species, which ultimately controls their reactivty profile.Most notably, standard alkyl radicals are nucleophilic and therefore do not react with electron rich aromatics and olefins. Electrophilic radicals display strong reactivity with these species but they are of limited synthetic value.

This project seeks to address this challenge by developing an innovative approach for radical ""umpolung"". In particular, we will demonstrate the integration of photoredox catalysis and boryl radical-mediated H-atom transfer catalysis, as a unique blueprint for the activation of alpha,alpha-diborylated alkalnes. This will generate alpha,alpha-diborylated radicals that, owing to their strong electrophilic character, will (i) react with electron rich aromatics and olefins and then (ii) enable diverge functionalization. In this way we will overcome the fundamental issue that nucleophilic alkyl radicals do not react with electron rich olefins/aromatics. This reactivity will streamline the preparation of many high-value but difficult to make aliphatic products, will be used in late-stage functionalizations and will substantially expand the fields of photoredox catalysis and boryl radical chemistry.

This research capitalizes on recent developments of the Leonori group that has experience in the design of methodologies based on both H-atom transfer and boryl radical reactivity.

The completion of such an innovative and ambitious project at RWTH Aachen University will be facilitated by generating, transferring, sharing and disseminating knowledge, and will enhance my future career following the training plan envisioned.
"

Fields of science (EuroSciVoc)

Keywords

Programme(s)

Topic(s)

Funding Scheme

HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European Fellowships

See all projects funded under this funding scheme

Call for proposal

(opens in new window) HORIZON-MSCA-2023-PF-01

See all projects funded under this call

Coordinator

RHEINISCH-WESTFAELISCHE TECHNISCHE HOCHSCHULE AACHEN
Net EU contribution
€ 189 687,36
Address
TEMPLERGRABEN 55
52062 Aachen
Germany
Region
Nordrhein-Westfalen Köln Städteregion Aachen
Activity type
Higher or Secondary Education Establishments
Links
Total cost
No data