期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 14, 期 29, 页码 8995-9005出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200800792
关键词
glycerol; homogeneous catalysis; palladium; phosphines; telomerization
资金
- ACTS-ASPECT
Glycerol is considered a potential renewable building block for the synthesis of existing as well as new chemicals. A promising route is the telomerization of 1,3-butadiene with glycerol leading to C-8 chain ethers of glycerol with applications in, for example, surfactant chemistry. Recently, we reported a new set of palladium-based homogeneous catalytic systems for the telomerization of 1,3-butadiene with glycerol and found that palladium complexes bearing methoxy-functionalized triphenylphosphine ligands are highly active catalysts capable of converting crude glycerol without any significant loss of activity. Herein, we present a detailed account of these investigations by reporting on the influence of the butadiene/glycerol ratio, temperature, and reaction time on product selectivity and activity allowing further optimization of catalyst performance. Maximum activity and yield were reached for high 1,3-butadiene/glycerol ratios at a temperature of 90 degrees C, whereas the selectivity for mono- and diethers of glycerol could be optimized by combining high reaction temperatures and short reaction times with low butadiene/glycerol ratios. Variation of the P-II metal precursors and the metal/ligand ratio showed that palladium precursors with halogen ligands gave unsatisfying results, in contrast to precursors with weakly coordinated ligands such as [Pd(OAc)(2)] and [Pd(acac)(2)]. [Pd(dba)(2)], the only Pd-0 precursor tested, gave the best results in terms of activity, which illustrates the importance of the ability to form a Pd-0 species in the catalytic cycle. Finally, base addition resulted in a shortening of the reaction time and most likely facilitates the formation of a Pd-0 species. Based on these results, we were able to realize the first attempts towards a rational ligand design aimed at a high selectivity for mono- and diether formation.
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