Radical Chemistry with the Hydrogen Atom Through Water Activation
This project aims to develop a novel photocatalytic method for water activation to transfer hydrogen into valuable compounds using metal-free phosphine-mediated radical processes.
Projectdetails
Introduction
Water activation, which allows the transfer of universally abundant hydrogen into value-added compounds, is an important research field in modern science. This task has been realized mainly by using transition-metal-based systems.
Novel Strategy
Herein we will use a conceptually novel mild water activation strategy which proceeds through a photocatalytic phosphine-mediated radical process. The active species in these processes is a metal-free R3P-OH2 radical cation intermediate where both hydrogen atoms are used in the following chemical transformation through sequential heterolytic (H+) and homolytic (H•) cleavage of the two O-H bonds.
Radical Intermediate
The R3P-OH radical intermediate provides an ideal platform to mimic the reactivity of a "free" hydrogen atom that can be directly transferred to various π-systems to give H-adduct C-radicals. These radicals are eventually reduced by a thiol cocatalyst, leading to the overall transfer hydrogenation of π-systems, with the two H-atoms of water ending up in the product. The driving force is the strong P-O bond formed in the phosphine oxide byproduct.
Research Focus
- Hydrogenation of alkenes, arenes, and hetero(arenes) will be investigated.
- Stereoselective reductions using chiral H-donors will be addressed.
- Deuteration and tritiation with D2O and T2O as formal reductants will be explored.
Methodology
Experimental studies will be supported by DFT calculations throughout the studies. Polar effects exerted by the H-donors will be studied, which will allow the design of more complex intramolecular and intermolecular reductive cascade reactions comprising C-C bond forming steps.
Reactivity Investigation
Reactivity of the novel R3P-OH radicals towards various functionalities will be systematically investigated, and the reactive functional groups will then be incorporated into cascade reactions.
Development of Reactions
Atom-economic radical H-transfer isomerization reactions that proceed with P-based catalysts will be developed. Finally, photoactive P-compounds will be used as mediators for water activation in hydrogen atom transfer radical chemistry.
Financiële details & Tijdlijn
Financiële details
Subsidiebedrag | € 2.500.000 |
Totale projectbegroting | € 2.500.000 |
Tijdlijn
Startdatum | 1-10-2024 |
Einddatum | 30-9-2029 |
Subsidiejaar | 2024 |
Partners & Locaties
Projectpartners
- UNIVERSITAET MUENSTERpenvoerder
Land(en)
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