Synthesis of primary amines from the renewable compound citronellal via biphasic reductive amination

Behr, Arno; Wintzer, Andreas; Lübke, C.; Müller, Matthias

doi:10.1016/j.molcata.2015.04.006

Cited by 20 publications

(20 citation statements)

References 32 publications

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“…Therefore, in combination with the water-soluble ligand TPPTS and the surfactant CTAC a biphasic solvent system was used to provide phase separation. The role of the surfactant was already investigated by our group in the reductive amination of citronellal also involving ammonia and CTAC was found to be slightly more efficient than CTAB [12]. Finally, an aqueous ammonia solution served as polar catalyst phase and toluene as organic phase for the starting material.…”

Section: Resultsmentioning

confidence: 95%

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Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Behr

Wintzer

2015

Chem Eng & Technol

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With the hydroaminomethylation of the natural compound limonene with ammonia an atom-economic method for the synthesis of primary amines is described. This tandem reaction allows the direct conversion of the unfunctionalized monoterpene to a valuable amine product. For the first time, ammonia served as substrate to result in a maximum primary amine yield of 25 %. To overcome unwanted side reactions, a biphasic solvent system was used, consisting of an aqueous catalyst phase and an organic product phase. As catalyst the water-soluble transition metal complex [Rh(cod)Cl] 2 /triphenylphosphine trisulfonate was chosen. In combination with the surfactant hexadecyltrimethylammonium chloride it provided a good phase interaction and the possibility for easy phase separation after the reaction.

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Section: Resultsmentioning

confidence: 95%

“…This method has also been applied by Drießen-Hölscher in the telomerization of butadiene with ammonia [11] and recently by us in the reductive amination of citronellal [12]. The implementation of water as solvent also offers the advantage of working in a more economically friendly environment [13].…”

Section: Introductionmentioning

confidence: 99%

Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Behr

Wintzer

2015

Chem Eng & Technol

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“…The (R)-isomer of citronellal is typically found in citronella while the essential oil of kaffir lime contains the (S)-isomer. Citronellyl amine can be synthesized from the amide [62], oxime [62], and from geranylnitrile [63]. An issue related to reductive amination of aldehydes with ammonia using transition metals as catalysts is the need to suppress side reactions (Figure 4).…”

Section: Reductive Amination Of Aldehydesmentioning

confidence: 99%

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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“…Recently, the synthesis of primary amines through direct reductive amination of aldehydes using ammonia as a nitrogen source has been explored. However, the transition metal-catalyzed reductive aminations have frequently been accompanied by unwanted side product(s) due to, for example, the reduction of aldehyde to an alcohol [8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Cross-Linked Cyclodextrins Bimetallic Nanocatalysts: Applications in Microwave-Assisted Reductive Aminations

et al. 2020

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The optimization of sustainable protocols for reductive amination has been a lingering challenge in green synthesis. In this context, a comparative study of different metal-loaded cross-linked cyclodextrins (CDs) were examined for the microwave (MW)-assisted reductive amination of aldehydes and ketones using either H2 or formic acid as a hydrogen source. The Pd/Cu heterogeneous nanocatalyst based on Pd (II) and Cu (I) salts embedded in a β-CD network was the most efficient in terms of yield and selectivity attained. In addition, the polymeric cross-linking avoided metal leaching, thus enhancing the process sustainability; good yields were realized using benzylamine under H2. These interesting findings were then applied to the MW-assisted one-pot synthesis of secondary amines via a tandem reductive amination of benzaldehyde with nitroaromatics under H2 pressure. The formation of a CuxPdy alloy under reaction conditions was discerned, and a synergic effect due to the cooperation between Cu and Pd has been hypothesized. During the reaction, the system worked as a bifunctional nanocatalyst wherein the Pd sites facilitate the reduction of nitro compounds, while the Cu species promote the subsequent imine hydrogenation affording structurally diverse secondary amines with high yields.

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Synthesis of primary amines from the renewable compound citronellal via biphasic reductive amination

Cited by 20 publications

References 32 publications

Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

Cross-Linked Cyclodextrins Bimetallic Nanocatalysts: Applications in Microwave-Assisted Reductive Aminations

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