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

Información del proyecto

BRAT

Identificador del acuerdo de subvención: 101150159

DOI

10.3030/101150159

Proyecto cerrado

Fecha de la firma de la CE 11 Abril 2024

Fecha de inicio 3 Junio 2024

Fecha de finalización 2 Junio 2026

Financiado con arreglo a

• Marie Skłodowska-Curie Actions (MSCA)

Coste total

Sin datos

Aportación de la UE

€ 189 687,36

Coordinado por

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)

Período documentado: 2024-06-03 hasta 2026-06-02

Resumen del contexto y de los objetivos generales del proyecto

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.

Trabajo realizado desde el comienzo del proyecto hasta el final del período abarcado por el informe y los principales resultados hasta la fecha

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.

Avances que van más allá del estado de la técnica e impacto potencial esperado (incluida la repercusión socioeconómica y las implicaciones sociales más amplias del proyecto hasta la fecha)

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.