Currently, a shift towards chemical products derived from renewable, biological feedstocks is observed more and more. However, substantial differences with traditional feedstocks, such as their "hyperfunctionalization," ethical problems caused by competition with foods, and problems with a constant qualitative/quantitative availability of the natural products, occasionally complicate the large-scale market entry of renewable resources. In this context the vast family of terpenes is often not taken into consideration, although the terpenes have been known for hundreds of years as components of essential oils obtained from leaves, flowers, and fruits of many plants. The simple acyclic monoterpenes, particularly the industrially available myrcene, provide a classical chemistry similar to unsaturated hydrocarbons already known from oil and gas. Hence, this Review is aimed at reviving myrcene as a renewable compound suitable for sustainable chemistry in the area of fine chemicals. The versatility of the unsaturated C(10)-hydrocarbon myrcene, leading to products with several different areas of application, is pointed out.

The transition-metal catalyzed telomerization of 1,3-dienes with different nucleophiles leads to the synthesis of numerous products, such as sugar ethers, substituted lactones, or terpene derivatives, which can be applied in the cosmetic and pharmaceutical industry as well as in polymers and flavors. The reaction can be controlled by the choice of the catalytic system, the feedstock, and the reaction conditions. Since telomerization was developed in 1967, there have been many efforts to utilize this reaction. Herein we give an overview of the versatility of telomerization based on examples from research and industry, particular emphasis is placed on catalyst and process development as well as mechanistic aspects.

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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.

Hydroamination is an elegant and atom economical reaction to convert alkenes into amines. One of the few technical realisations of this reaction is the hydroamination of myrcene to diethylgeranyl-A C H T U N G T R E N N U N G amine, an important precursor of (À)-menthol. However, this so-called "Takasago process" is catalysed by high amounts of alkali metals, especially lithium, which makes it a relatively expensive approach. In the present work, the hydroamination of myrcene with morpholine is catalysed by palladium complexes with bidentate ligands such as bis(diphenylphosphino)butane (DPPB) or bis(2-diphenylphosphinophenyl) ether (DPEphos). The systematic optimisation of the reaction parameters under single-phase conditions led to yields of the 1,4-adducts of higher than 90%. The only side products proved to be the telomers of myrcene, whose formation could be decreased by using appropriate reaction conditions. The method of temperature-dependent solvent systems was successfully applied to separate the palladium catalyst from the amines with a palladium leaching lower than 1.0%.