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-furyl-phosphines 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).