Diphosphines of dppf‐Type Incorporating Electron‐Withdrawing Furyl Moieties Substantially Improve the Palladium‐Catalysed Amination of Allyl Acetates

Highly active Pd/diphosphine catalytic systems incorporating new, air‐stable ferrocenyl‐furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h −1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h −1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of economical (resource‐ and energy‐saving) and sustainable chemistry (high selectivity, no additive, low metal content, and thus easier purification).