Telomerization of 1,3-butadiene with alcohols catalyzed by homogeneous palladium(0) complexes in the presence of mono- and diphosphine ligands

The homogeneous telomerization of 1,3-butadiene with alcohols for the selective synthesis of linear octadienyl ethers in the presence of catalysts prepared in situ from palladium(0) bis-dibenzylidene-acetone and different mono- and diphosphine ancillary ligands is described. With monophosphines, a correlation between basicity as well as steric hindrance of the ligand and activity and selectivity of the resulting catalyst was found. When diphosphines were used, the effect of the bite of the chelating ligand, as well as its basicity and steric hindrance on the activity and selectivity of the process was studied and discussed in terms of the relative stability of the metallacyclo moieties involved in the catalytic cycle. The above results have allowed to gain more light on the reaction mechanism. (C) 1999 Elsevier Science B.V. All rights reserved.