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Ethenolysis involves the CM of ethylene and an internal olefin to generate terminal olefins. The ethenolysis of soybean oil
to produce 9-decenoic acid is of significant interest to the chemical industry as an antimicrobial agent and as a monomer
for polymer-industry applications (24–26). More recently, reports on the synthesis of additional biologically active molecules
involving CM reactions of ethylene with internal olefins have been published as well (27). Given the high reactivity of Piers'
catalysts with ethylene, we were interested in exploring their use for the ethenolysis of seed oils. This use is important
as natural seed oils represent a renewable source of olefinic raw materials that can provide atom-efficient and environmentally
friendly products. The affordability of these olefinic sources, coupled with their worldwide availability and inherent functionality,
has already contributed to their use in several areas (24). Olefin metathesis offers new and exciting opportunities for the
conversion of these unsaturated seed oils into commodity chemicals that can have wide-ranging applications.
Reaction 3
Ethenolysis can be complicated by secondary metathesis reactions (secondary processes generate undesired internal olefins)
and by the self-metathesis of internal olefins. For an ethenolysis of methyl oleate model reaction, see Reaction 1, along
with a competing self-metathesis process, see Reaction 2.
Reaction 4
Piers' Catalyst 1b (see Figure 1) demonstrated very good selectivity for the desired ethenolysis products, while Piers' Catalyst
2b (see Figure 1) led to the formation of significant amounts of self-metathesis products, and thus, low ethenolysis selectivity.
Figure 6 (ALL FIGURES ARE COURTESY OF THE AUTHORS.)
The same trend was observed for Grubbs Catalysts 3 and 4 (see Figure 4) (28). The catalytic performance of Piers' Catalyst
1b and Grubbs Catalyst 3 for the ethenolysis of methyl oleate were compared at 20 °C and 40 °C, using toluene as the solvent
and 0.02 mol% catalyst under 150 psi ethylene (see Figure 6). Data points were taken at 2 h (29). As shown in Figure 6, Catalysts
1b and 3 showed similar efficiency at 40 °C. At 20 °C, however, Catalyst 1b is much more active than Catalyst 3.
Ring-closing metathesis
Figure 7 (ALL FIGURES ARE COURTESY OF THE AUTHORS.)
RCM is one of the most used metathesis reactions for the synthesis of biologically active molecules. Studies in the Piers'
group and at Materia have shown the advantage of Piers' catalysts. The high efficiency of Piers' Catalyst 2a (see Figure 1)
for RCM at low temperature (0 °C) was initially reported by Piers and coworkers (6, 7). Using RCM of diethyl diallymalonate
as a model reaction (see Reaction 3), they have shown that Catalyst 2a (see Figure 1) outperformed Catalyst 1a (see Figure
1) as well as the other olefin-metathesis catalysts.
Richard L. Pederson, PhD, is director of fine chemicals R&D at Materia, Inc., 60 N. San Gabriel Blvd., Pasadena, CA 91107, tel. 626.584.8400, fax 626.584.1984
Articles by Richard L. Pederson, PhD
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