Short Communication Copper(II) catalyzed allylic amination of terpenic chlorides in water Brahim Boualy a , Mohamed Anouar Harrad a , Soufiane El Houssame b , Larbi El Firdoussi a, ⁎, Mustapha Ait Ali a , Abdallah Karim a a Equipe de Chimie de Coordination et Catalyse, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, 40001 Marrakech, Morocco b Université Hassan 1 er , Faculté Polydisciplinaire de Khouribga, BP: 145-25000 Khouribga, Morocco abstract article info Article history: Received 26 May 2011 Received in revised form 15 December 2011 Accepted 19 December 2011 Available online 27 December 2011 Keywords: Allylic amination Allylic chlorides Copper Water Monoterpenes A highly efficient method for the synthesis of allylic amines from terpenic chlorides by cheap copper (II) as catalyst in water has been developed. Allylic chlorides react with high regioselectivity in the presence of sec- ondary amines, under mild conditions to give N-allylic amines in excellent yields. © 2011 Elsevier B.V. All rights reserved. 1. Introduction Allylic amines are important products found in many naturally oc- curring compounds such as gabaculin [1], oryzoxymicin [2], and cyto- sinine [3]. The development of easier and selective methods for the synthesis of allylic amines merits thorough investigation [4], since di- rect reaction require rather drastic conditions [5]. Transition metal- promoted allylic amination of alkenes offers an attractive route to prepare amines via C\N bond formation [6]. However, complexes of palladium are found to be most effective for selective processes, al- though complexes of iron, nickel, and copper are also used for allylic amination [7–9]. The catalytic activity of a number of copper complexes and salts toward allylic amination of alkenes using phenylhydroxylamine as the nitrogen fragment donor has been investigated [10]. The copper (I) complex [Cu(CH 3 CN) 4 ]PF 6 catalyzes the allylic amination of al- kenes by aryl hydroxylamine in fair to moderate yields [6]. Recently Clark et al. reported that asymmetric allylic amination can be achieved by reaction of an alkene with a peroxycarbamate cat- alyzed by a chiral copper bis-oxazoline complex [11]. An efficient method to perform the allylic substitution in water has been reported [12–14]. It should be noted that, Sinou et al. and Kobayashi et al. have reported that palladium-catalyzed alkylation also occurred in water in the presence of non-water-soluble ligands, but the addition of surfactants such as cetyltrimethylammonium bro- mide was required [15,16]. Moreover, Feuerstein et al. showed that Tedicyp–palladium complex provides a convenient catalyst for the al- lylic amination reaction in water [17]. A large number of biologically active natural compounds consist of a nitrogen-containing heterocycle and occupy a leading position in medicinal therapy [18,19]. In particular, allylic aminated terpenoids because of their effects of inhibiting tumor cell growth in vivo and vitro [20–22] and it serves as a tool for the synthesis of new enantio- merically pure compounds [23–25]. Baruah et al. have developed a new method for the conversion of allylic halides to allylic amines by using a mixture of copper (II) per- chlorate and copper metal [26]. They found significant differences in the product ratios of the isomeric corresponding allylic amines formed. In the course of our studies on monoterpenes and their deriva- tives, we have recently reported an extremely efficient method for the preparation of various allylic terpenic chlorides [23]. Following our catalysis objective on the coupling of various amines and natural allylic compounds [27], we herein, with a view to extend the poten- tial use of these terpenic chlorides, focused our efforts on the allylic amination reaction using copper complexes. Our results show that monoterpenic chlorides react to give the corresponding allylic amines with a good to excellent yields. The optical purity of the reaction products has been also discussed. The use of water as solvent for this reaction is of interest in sustainable chemistry. It provides in ad- dition noticeable advantages in terms of economical, environmental and safety reasons. Catalysis Communications 19 (2012) 46–50 ⁎ Corresponding author. Tel.: + 212 524 434649; fax: + 212 524 437408. E-mail address: elfirdoussi@ucam.ac.ma (L. El Firdoussi). 1566-7367/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2011.12.019 Contents lists available at SciVerse ScienceDirect Catalysis Communications journal homepage: www.elsevier.com/locate/catcom