Hydroaminomethylation of Isoprene: Recycling of the Homogeneous Rhodium Catalyst in Aqueous Biphasic Systems

Behr, Arno; Reyer, Sebastian; Manz, Vanessa

doi:10.1002/cite.201100106

Cited by 9 publications

(8 citation statements)

References 25 publications

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“…None of the hydroaminomethylations mentioned above consist of a hydroformylation of conjugated 1,3‐dienes but rather isolated terminal double bonds. The only reported hydroaminomethylations of conjugated 1,3‐dienes are isoprene and cyclopentadiene . Both reactions suffer from low regioselectivity of the hydroformylation, on the one hand, and low catalytic activity of rhodium if applied to 1,3‐dienes, on the other .…”

Section: Methodsmentioning

confidence: 99%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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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.

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Section: Methodsmentioning

confidence: 99%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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“…Hydroformylation of the internal double bonds is much more difficult than the terminal bonds, thus it is not surprising that the examples mentioned above are related to isolated terminal double bonds. In the only reported hydroaminomethylation of a conjugated terpene [81] regioselectivity in hydroformylation was low along with low catalytic activity per se explained by formation of relatively stable η3-allyl-Rh complexes [78].…”

Section: Hydroaminomethylation Of Olefin Bonds In Terpenesmentioning

confidence: 98%

Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

2018

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This review fills an apparent gap existing in the literature by providing an overview of the readily available terpenes and existing catalytic protocols for preparation of terpene-derived amines. To address the role of solid catalysts in amination of terpenes the same reactions with homogeneous counterparts are also discussed. Such catalysts can be considered as a benchmark, which solid catalysts should match. Although catalytic systems based on transition metal complexes have been developed for synthesis of amines to a larger extent, there is an apparent need to reduce the production costs. Subsequently, homogenous systems based on cheaper metals operating by nucleophilic substitution (e.g., Ni, Co, Cu, Fe) with a possibility of easy recycling, as well as metal nanoparticles (e.g., Pd, Au) supported on amphoteric oxides should be developed. These catalysts will allow synthesis of amine derivatives of terpenes which have a broad range of applications as specialty chemicals (e.g., pesticides, surfactants, etc.) and pharmaceuticals. The review will be useful in selection and design of appropriate solid materials with tailored properties as efficient catalysts for amination of terpenes.

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“…By using morpholine, a secondary amine, the intermediate aldehyde undergoes reductive amination. The main products of this tandem reaction are saturated C6‐amines . By using the Rh/TPPTS system in water, the catalyst can be recycled by decanting the nonpolar organic product phase (Figure , bottom reaction).…”

Section: C5 Moleculesmentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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Hydroaminomethylation of Isoprene: Recycling of the Homogeneous Rhodium Catalyst in Aqueous Biphasic Systems

Cited by 9 publications

References 25 publications

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

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