Telomerization is a versatile tool for synthesizing unsaturated ethers, amines and other molecules starting from 1,3‐dienes and respective nucleophiles. The homogeneously catalyzed reaction has been the subject of academic and industrial research for over 50 years, offering a broad variety of substrates, catalysts and process concepts. This Minireview presents the advances and developments in this field over the last decade. The focus was on the conversion of renewable resources, the synthesis of promising new products and the development of efficient process concepts to combine these.

A catalytic system was developed to enable the use of industrially available terpenes (e.g., β‐myrcene, β‐farnesene) in hydroaminomethylation to obtain renewable building blocks for surfactants in two steps. This homogeneously catalyzed tandem reaction includes both hydroformylation and enamine condensation steps, followed by hydrogenation. Under the optimized conditions, the Rh/1,2‐bis(diphenylphosphino)ethane catalytic system delivers products in high yields (70 %) after short reaction times (3 h) with unprecedentedly high turnover frequency (TOF) values for the hydroformylation of 1,3‐dienes of over 739 mol mol−1 h−1. This is the highest TOF reported to date for the hydroformylation of a 1,3‐diene. Furthermore, regioselectivities of 97 % and above were observed in the hydroformylation step, which is extraordinarily high for the conversion of 1,3‐dienes. The terpene‐derived amines obtained were further functionalized to quaternary ammonium compounds that were found to show surface activity quite similar to that of industrially available quaternary ammonium compounds. The hydroaminomethylation of terpenes achieves higher step efficiency than industrial means and makes use of an alternative, renewable feedstock to synthesize more environmentally friendly surfactants.

Biphasic water-based solvent systems offer the opportunity of efficient recycling of homogeneous catalysts. Water separates well from most organic solvents; therefore, water-soluble catalysts can be immobilized in this phase. Furthermore, water can substitute hazardous and environmentally unfriendly organic solvents in these systems. Within industry only the Ruhrchemie/Rhône-Poulenc process uses plain water to immobilize the homogeneous catalyst for the hydroformylation of propene. Yet for more hydrophobic substrates, no water-based system has been commercialized. This review will summarize recent developments in the field of water-based recycling strategies. Topics in this field are the intensification of the mixing process, the use of thermomorphic solvent systems, and the employment of several additives, like alcohols and surfactants. Continuously operated processes for these recycling strategies will be presented and discussed.

Turning down the bed for homogenous catalysts: the use of dimcarb as a reactive ionic liquid, offers the opportunity to carry out different homogeneously transition metal catalyzed aminations without using any solvent, while at the same time efficient catalyst recycling is possible.

Die homogene Katalyse zeichnet sich gegenüber der heterogenen Katalyse durch höhere Selektivität und Aktivität bei gleichzeitig milderen Reaktionsbedingungen aus; die Abtrennung der teuren Übergangsmetallkatalysatoren von den Reaktionsprodukten ist jedoch schwierig. Temperaturgesteuerte Lösungsmittelsysteme, die bei geringer Temperatur in zwei Phasen vorliegen und bei Temperaturerhöhung ein homogenes, einphasiges Lösungsmittelsystem ausbilden, ermöglichen eine Reaktionsführung ohne Stofftransportlimitierungen. Durch Abkühlung bildet sich erneut ein Zweiphasensystem aus, bei dem im Idealfall eine Phase das Produkt und die andere den Katalysator enthält.

Tandem‐catalyzed hydroaminomethylation is a useful tool for synthesizing linear amines from olefins and amines in an atom‐efficient manner. To enable the coupling of highly functionalized, hydrosoluble amines with non‐water‐soluble olefins, this reaction must be transferred to aqueous biphasic solvent systems. In this work, we systematically evaluate reaction conditions to provide a selective hydroaminomethylation of 1‐octene with diethanolamine as model substrates. Although water is both the condensation side product and the solvent, yields of 79% were achieved using a catalytic system consisting a rhodium precursor and a sulfonated diphosphine ligand. This approach was applied to other functionalized amines, proving this concept is a suitable tool for the catalytic alkylation of highly functionalized amines.magnified image

An ovel, atom efficient, orthogonal tandem catalysisw as developed yieldinga cyloin products( a -hydroxyk etones) directlyf rom olefins under hydroformylation conditions.T he combination of am etal-catalysed hydroformylation anda n organocatalysed acyloin reactionp rovides three atom efficient C À Cb ondf ormations to linear, multifunctional molecules via linkage of the intermediate n-aldehydes.A dditionally,t he rhodium catalyst system gives ah igh n/bra ratio with an exclusive conversion of the terminal doubleb ond in the hydroformylation and the n-aldehydes are converted selectively to theiracyloins.

Using the water-soluble N-methylglucamine and the non-polar β-myrcene in a biphasic telomerisation with the amphiphilic TPPMS ligand, new surfactants are obtained.