Bis(perfluoroalkyl) Phosphino-Oxazoline: A Modular, Stable, Strongly π‑Accepting Ligand for Asymmetric Catalysis

A new class of stable, strongly π-accepting and modular bis­(perfluoroalkyl)-phosphine-oxazoline ligands (FOX) as CO mimics was prepared. It was demonstrated that these ligands, when coordinated to palladium catalysts, promote the asymmetric alkylation of monosubstituted allyl substrates with excellent regio- and enantioselectivity. Solid and solution structure analysis of the FOX-ligated Pd-allyl intermediate reveals that the combination of relative steric and strong <i>trans</i> influences presented by the P­(CF<sub>3</sub>)<sub>2</sub> moiety gave rise to the excellent selectivity.