[PFPforNi] Harnessing perfluorinated phosphine ligands to accelerate nickel catalysis
Ente: European Commission
Scadenza: 2028-09-30
Importo max: 260.347,92 EUR
Paese: EU
Descrizione
Ligands are crucial to endow metals with specific catalytic properties, and ligand design with fine tuning has allowed chemists to realize new transformations and optimize existing ones. In recent years, N-heterocyclic carbenes and dialkyl-ortho-biaryl phosphines offered two striking examples: these neutral ligands reported in the 1990s are nowadays utilized in a plethora of metal-catalyzed transformations in pharmaceutical, agrochemical, fine chemistry and polymer sectors. In particular, the class of dialkyl-ortho-biaryl phosphines, initially developed for Pd-catalyzed Suzuki and C–N coupling reactions, has been widened with variations focused mostly on the biaryl rings, and is now routinely used with several metals in a vast array of C-C and C-X bond-forming reactions. As a result of continuous efforts in ligand design, the chemical space occupied by phosphines ligands is well covered including the bulky, electron-rich triadamantyl and di-tert-alkyl phosphines. However, there remains a significant gap in the P(III) ligands with low σ-donating and high π-accepting abilities, electronically comparable to phosphites, halophosphines and even CO. As early as 2003, computational analysis clearly identified this gap as a very interesting area to explore, but no progress has been made to date.
In this PFPforNi (Harnessing perfluorinated phosphine ligands to accelerate nickel catalysis, Dr Attunuri Nagireddy (AN), mentored by Dr Allegra Franchino (AF) at Durham University, will target exactly this unchartered chemical space, by preparing for the first time mono, bis and tris perfluoro-tert-butyl phosphines, which possess a unique, hitherto unexplored combination of steric and electronic properties. We anticipate that these bulky, electron-poor ligands will stabilize low-valent Ni(0) centres, thanks to their steric shielding and π-accepting ability, and therefore aid challenging reductive eliminations, with benefits in a plethora of Ni-catalyzed cross couplings.
Settori: nickel, phosphines, reductive elimination, fluorination
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