Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives

Ferrocenylphosphines added to [Pd(µ‐Cl)(η³‐C₃H₅)]₂ dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1′‐bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial interest. Copyright © 2006 John Wiley & Sons, Ltd.