TETRAHEDRON LETTERS Tetrahedron Letters 44 (2003) 1221–1225 Pergamon Heck reaction of aryl halides with linear or cyclic alkenes catalysed by a tetraphosphine/palladium catalyst Florian Berthiol, Henri Doucet* and Maurice Santelli* Laboratoire de Synthe `se Organique associe ´ au CNRS, Faculte ´ des Sciences de Saint Je ´ro ˆme, Avenue Escadrille Normandie -Niemen, 13397 Marseille Cedex 20, France Received 18 November 2002; accepted 8 December 2002 Abstract—cis,cis,cis -1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C 3 H 5 )] 2 system catalyses efficiently the Heck reaction of aryl halides with linear alkenes such as pent-1-ene, oct-1-ene or dec-1-ene. Selectivities up to 70% in favour of E -1-arylalk-1-ene isomers can be obtained. In the presence of cyclic alkenes the selectivities of the reactions strongly depends on the ring size. Addition to cyclohexene or cycloheptene led mainly to 1-arylcycloalk-3-ene derivatives. On the other hand, addition to cyclooctene led to 1-arylcycloalk-1-ene adducts. © 2003 Elsevier Science Ltd. All rights reserved. Palladium-catalysed Heck vinylation reaction is one of the most powerful method for the formation of CC bonds. 1 The efficiency of several catalysts for the reac- tion of aryl halides with acrylates has been studied in detail. On the other hand, the reaction in the presence of simple linear or cyclic alkenes such as oct-1-ene or cyclooctene has attracted less attention. 2,3 A few ligands have been successfully employed for the reaction in the presence of such substrates. The most popular one is triphenylphosphine, but the catalysts formed by associ- ation of this ligands with palladium complexes is gener- ally not very efficient in terms of ratio substrate/ catalyst 2a,3a–d and 1–10% of this catalyst must often be used. For a few years, some more robust and more efficient catalysts such as palladacycles 4 have been tested with these substrates. For example, Beller et al. have reported that the palladacycle [Pd(o -tol)(OAc)] 2 is very efficient for the reaction of 4-bromoacetophenone with cyclopentene or cyclohexene. 3f In the monophos- phine ligand series, interesting results have been reported recently by Fu et al. They described that the ligand P(t -Bu) 3 is an efficient catalyst for the reaction of 4-chloroacetophenone with hex-1-ene even at room temperature. 2d If monophosphine ligands or palladacy- cles have been successfully used for the reaction with these alkenes, to the best of our knowledge, the efficiency of tetraphosphine ligands has not been demonstrated. The nature of phosphine ligands on complexes has an important influence on the rate of catalysed reactions. In order to obtain highly stable palladium catalysts, we have prepared the new tetraphosphine ligand, 5 cis, cis,cis - 1,2,3,4 - tetrakis(diphenylphosphinomethyl)cyclo- pentane or tedicyp 6 (Fig. 1) in which four diphenyl- phosphino groups are stereospecifically bound to the same face of a cyclopentane ring. The presence of these four phosphines close to the metal centre seems to increase the coordination of the ligand to the metal and Figure 1. Scheme 1. * Corresponding authors. Tel.: 00-33-4-91-28-84-16; fax: 00-33-4-91-98-38-65 (H.D.); Tel.: 00-33-4-91-28-88-25 (M.S.); e-mail: henri.doucet@ univ.u-3mrs.fr; m.santelli@univ.u-3mrs.fr 0040-4039/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved. PII:S0040-4039(02)02788-0