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

Projektinformationen

BRAT

ID Finanzhilfevereinbarung: 101150159

DOI

10.3030/101150159

Projekt abgeschlossen

EK-Unterschriftsdatum 11 April 2024

Startdatum 3 Juni 2024

Enddatum 2 Juni 2026

Finanziert unter

• Marie Skłodowska-Curie Actions (MSCA)

Gesamtkosten

Keine Daten

EU-Beitrag

€ 189 687,36

Koordiniert durch

RHEINISCH-WESTFAELISCHE TECHNISCHE HOCHSCHULE AACHEN
Germany

Periodic Reporting for period 1 - BRAT (Development of a boryl radical-mediated H-atom transfer umpolung blueprint to make nucleophilic radicals behave as electrophilic species)

Berichtszeitraum: 2024-06-03 bis 2026-06-02

Zusammenfassung vom Kontext und den Gesamtzielen des Projekts

The main objective of this project was the development of a novel platform for radical polarity inversion ("umpolung"), enabling the efficient functionalisation of electron-rich aromatics and olefins. The overarching goal was to combine photoredox catalysis with boryl radical-mediated hydrogen atom transfer catalysis to generate electrophilic α,α-diborylated radicals from readily available α,α-diborylated alkanes.

This approach addresses a fundamental limitation in radical chemistry, namely the inability of conventional nucleophilic alkyl radicals to react with electron-rich π-systems. By generating highly electrophilic carbon-centred radicals, the methodology enables efficient bond formation with electron-rich aromatics and olefins, followed by diverse downstream functionalisation.

The project builds upon the Leonori group's expertise in photoredox catalysis, hydrogen atom transfer processes, and boryl radical chemistry. The successful implementation of this strategy is expected to provide streamlined access to valuable aliphatic molecular architectures, facilitate late-stage functionalisation, and significantly expand the synthetic utility of radical chemistry. Furthermore, the project contributes to knowledge generation and dissemination while supporting advanced scientific training and career development at RWTH Aachen University.

Arbeit, die ab Beginn des Projekts bis zum Ende des durch den Bericht erfassten Berichtszeitraums geleistet wurde, und die wichtigsten bis dahin erzielten Ergebnisse

We have made good process, demonstrating the propensity of amine-ligated boryl radicals to undergo a large number of chemical reactions including the fragmentation of cyclic systems. This has significantly expanded the toolbox of reactions that can be used for the synthesis of small molecules building blocks.

Fortschritte, die über den aktuellen Stand der Technik hinausgehen und voraussichtliche potenzielle Auswirkungen (einschließlich der bis dato erzielten sozioökonomischen Auswirkungen und weiter gefassten gesellschaftlichen Auswirkungen des Projekts)

The project has delivered substantial scientific impact and made a clear contribution to advancing the state of the art in synthetic organic chemistry. It addressed long-standing limitations in the functionalization of nitrogen heterocycles such as aziridines and it has provided a new retrosynthetic logic for the synthesis of key organic structures. Key scientific and technological achievements include the validation of this boryl radical reactivity concepts, the elucidation of its mechanistic basis, and the demonstration of its applicability to structurally diverse and medicinally relevant substrates.