APPLIED ORGANOMETALLIC CHEMISTRY Appl. Organometal. Chem. 2006; 20: 845–850 Published online 22 September 2006 in Wiley InterScience (www.interscience.wiley.com) DOI:10.1002/aoc.1130 Materials, Nanoscience and Catalysis Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives Duc Hanh Nguyen 1 , Martine Urrutigo¨ ıty 1 *, Aziz Fihri 2 , Jean-Cyrille Hierso 2 *, Philippe Meunier 2 and Philippe Kalck 1 1 Laboratoire de Catalyse et Chimie Fine, Ecole Nationale Sup ´ erieure des Ing ´ enieurs en Arts Chimiques et Technologiques, 118 route de Narbonne 31077 Toulouse, France 2 Laboratoire de Synth ` ese et Electrosynth ` ese Organom ´ etalliques (UMR-CNRS 5188), Universit ´ e de Bourgogne 9 avenue Alain Savary, 21078 Dijon, France Received 24 March 2006; Revised 12 April 2006; Accepted 18 May 2006 Ferrocenylphosphines added to [Pd(μ-Cl)(η 3 -C 3 H 5 )] 2 dimeric precursor produce efficient cat- alysts 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. KEYWORDS: allylic amination; monoterpenes; ferrocenylphosphine; palladium catalysis INTRODUCTION A large number of biologically active natural compounds consist of a nitrogen-containing heterocycle and occupy a leading position in medicinal therapy. 1,2 The direct synthetic procedures for amine synthesis, such as nucleophilic substitutions of organic halides by amines, cyanides or more generally by nitrogen-containing products, result in the co- production of abundant quantities of salts. In the general context of atom economy and sustainable chemistry, a base- free catalytic approach is particularly appropriate to convert plentiful starting materials such as alcohols or acetates. 3–6 In the course of our studies on monoterpenes and their oxygenated derivatives which are of much interest in perfumery, for artificial flavoring and in the pharmaceutical industry, we previously showed a chemoselective way to produce lactones from different monoterpenic alcohols *Correspondence to: Martine Urrutigo¨ ıty, Laboratoire de Catalyse, Chimie Fine et Polym` eres, Toulouse or Jean-Cyrille Hierso, Laboratoire de synth` ese et el´ ectrosynth` ese organom´ etallique, Dijon. E-mail: martine.urrutigoity@ensiacet.fr; jean-cyrille.hierso@u-bourgogne.fr through palladium-catalyzed tandem carbonylation. 7 With a view to extend the potential use of these naturally occurring alkenes, we focused our efforts on the amination of those containing an allylic function in order to have a direct access to lactames from allylic amines, as depicted in Fig. 1, with the cyclocarbonylation of geranylamine. Phosphorus-containing palladium complexes furnish effi- cient catalytic systems to allow access to unsaturated amines by allylic substitution. 8–10 It has been proved that key inter- mediates such as (η 3 -allyl)palladium complexes are involved in amine alkylations, and that the phosphine ligands exert a profound influence on the reaction rate. Recent studies have shown that multidentate ligands, such as the tetraphos- phine ligand tetrakis(diphenylphosphino)cyclopentane, 11 – 13 combined with palladium provide suitable systems for allylic amination with high turnover numbers (TON) and good rates. The present study is devoted to the investigation of catalytic allylic amination, in which the palladium precursor is stabi- lized by di-, or tetraphosphine ligands incorporating the fer- rocenyl framework. To date, only a few investigations of the performances in allylic substitution of this type of polydentate ligands have been reported in the literature. 11 – 13 Our results Copyright  2006 John Wiley & Sons, Ltd.