Addition and Telomerisation Reactions

A state-of-the-art account has been given on the role of q -allyl Pd complexes in diene oligomerisations and (mainly) te1omerisations.25 The 1,4-acetoxychlorination of conjugated dienes is catalysed by Pd(0Ac)2/L1Cl/ LiOAc/HOAc in the presence of benzoquinone and proceeds stereoselectively cis 

N-C bonds are broken by Pd catalysts in the telomerisation of butadiene with ally diethylamine to give mainly (47). The reaction of isoprene with HNEt2 in the presence of cationic Pd complexes gives mainly (50-70%) head-to-head telomers. Alkane- and arene sulphonamides react with butadiene like primary amines.Isoprene reacts with water (Pd catalyst, 90 0) to give a mixture of terpenols a catalyst supported on a phosphinated resin is prone to leaching. Butadiene reacts with cyclohexenone to give (48) in moderate yield.  

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R. Kh. Freidlina and F. K. Velichko, Synthetic Applications of Homolytic Addition and Telomerisation Reactions of Bromine-containing Addends with Unsaturated Compounds Containing Electron-withdrawing Substituents , Synthesis, 1911, 145. 

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