1-Decene, reaction with ruthenium

The methatesis of vegetable oils with ethylene is a very interesting way to obtain new unsaturated structures to be transformed into new polyols via the epoxidation - alcoholysis route. Trioleine was used as a model compound (the triester of glycerol with oleic acid), the methatesis reaction with ethylene being catalysed by a special ruthenium catalyst [72]. The resulting triglyceride, with terminal double bonds, after removal of the 1-decene formed, is transformed into polyols by epoxidation, followed by alcoholysis with methanol (reactions 17.27 and 17.28). 

Catalytic hydroboration is a new methodology of great synthetic potential. The reaction is usually carried out with catecholborane in the presence of rhodium, palladium, iridium and ruthenium compounds.2 In contrast to olefins, very little is known on catalytic hydroboration of conjugated dienes and enynes. Our earlier studies on the uncatalyzed monohydroboration of conjugated dienes,6 reports on the hydroboration of 1-decene with catecholborane catalyzed by lanthanide iodides,7 and monohydroboration of 1,3-enynes in the presence of palladium compounds,8 prompted us to search for other transition metal catalysts for monohydroboration of conjugated dienes and enynes 9 10... 

Metathesis has been applied in oleochemistry for many years, but only fairly recently technical realization comes within reach [33, 34]. As typical catalysts, ruthenium carbene complexes of the Grubbs type are applied because of their very high activity (turnover numbers up to 200 000). In principle, oleochemical metathesis can be divided into two different types in self-metathesis the same fatty substrate reacts with itself and in cross-metathesis a fatty substrate reacts with, for example, a petrochemical alkene. The simplest case, the self-metathesis of methyl oleate forms 9-octadecene and dimethyl 9-octadecenedioate. The resulting diester can be used along with diols for the production of special, comparatively hydrophobic, polyesters. An interesting example of cross-metathesis is the reaction of methyl oleate with an excess of ethene, so-called ethenolysis. This provides two produds, each with a terminal double bond, 1-decene and methyl 9-decenoate (Scheme 3.3). 

With methyl oleate, 53% yield of the terminal alcohol was observed. With unmodified internal olefins (2-decene, 2-tridecene, 4-octene), even higher regioselectivities in favor of the terminal alcohol could be achieved l/b up to 12 1). Proof was given that both rhodium and ruthenium complexes catalyze the isomerization-hydroformylation-hydrogenation reaction in a cooperative manner. 

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