Telomerization of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems

Abstract

Telomerization of common petrochemical 1,3‐dienes such as butadiene and isoprene have long been successful with different nucleophiles; however, the telomerization of the C10 hydrocarbon myrcene was not known until now. Herein, the first telomerization of the monoterpene myrcene with diethylamine is discussed, which provides an atom‐economical way of generating C20 amines in a single step. Variation of the palladium precursors and phosphorous ligands and optimization of solvent and additives led to the optimum catalyst system [Pd(MeCN)4](BF4)2/PPh3. By using a thermomorphic solvent system, the Pd complex can be easily separated with low leaching values.

Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

“…During the solvent screening, it turned out that polar solvents like DMF or acetonitrile, which form convenient TMS systems with long chain alkanes and have shown potential in several other catalytic reactions, 42,43 only give low yields in piperylene hydroformylation. Next to come is the implementation of a convenient recycling strategy.…”

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

“…In particular, those terpenes industrially available, which are derived mostly from turpentine, form an attractive group of substrates. Behr et al recently used the renewable 1,3-diene myrcene in the telomerization with diethylamine, for instance [18]. The monoterpene myrcene is easily obtained from b-pinene, sourced from the crude resin of pines, by pyrolysis, and is currently already used in many different applications.…”

“…1,3-Butadiene is most often used as the conjugated diene, since it is cheap, readily available and provides a linear octadienyl chain. The use of other dienes, such as isoprene [13][14][15][16], piperylene [17] and myrcene [18,19], has also been described, but they have been far less commonly studied. Such substituted telogens come with an additional selectivity challenge as many more isomers can potentially be obtained, which is illustrated for isoprene in Fig.…”

Construction Kit for the Solvent Selection in Homogeneous Catalyzed Reactions

“…Beispiele sind die Hydroformylierung [67], die Hydroaminomethylierung [68], Cooligomerisierungen [69,70] und die Telomerisation [71]. Auch für das Recycling von Biokatalysatoren konnte das Konzept der TML-Systeme erfolgreich angewendet werden [72]. Über die Anwendung von TML-Systemen in der homogenen Katalyse wurde eine umfangreiche Übersicht erstellt [73].…”