Specific Polar Solvents as Organocatalysts for the Hydrosilylation of Isoprene

Behr, Arno; Reyer, Sebastian; Brunsch, Yvonne; Manz, Vanessa

doi:10.1055/s-0031-1289669

Cited by 4 publications

(4 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The combination of Rh(acac)(cod) as a precursor and triphenylphosphine (PPh 3 ) as a ligand is highly promising to form the active RA catalyst, considering the reaction speed and selectivity, as demonstrated recently. − Since PPh 3 is a robust and comparatively cheap ligand, its application is highly beneficial. − To keep the experimental effort as low as possible, while still achieving satisfying performance in continuous operation, promising solvents identified from previous hydroformylation investigations were applied. − …”

Section: Resultsmentioning

confidence: 99%

“…While the chosen transition-metal catalyst, built upon Rh(acac)(cod) and PPh 3 , is highly soluble in DMF and the desired product amine is rather nonpolar, DMF is used as a polar solvent to accommodate the catalyst complex. TMS consisting of the polar solvent DMF and alkanes as nonpolar solvents have shown successful results in the hydroformylation of 1-dodecene. − However, the nonpolar solvent cannot be taken from literature, since the substrate amine and the coproduct water from the reaction are two components that can act as a phase mediator between polar and nonpolar phases. Hence, the nonpolar solvent needs to be adapted to the different solubility properties to ensure an efficient phase separation.…”

Section: Resultsmentioning

confidence: 99%

“…Brunsch et al − and Zagajewski et al − have shown in several small-scale batch experiments and in continuous operations that a TMS consisting of dimethylformamide (DMF) as a polar solvent and n -dodecane as a nonpolar solvent is a promising combination for the selective hydroformylation of higher olefins to the corresponding linear aldehydes, when a proper catalyst is applied. Based on this research, certain crucial steps for a process development applying TMS for the recovery of transition-metal catalyst were identified: identification of a suitable combination of transition metal and ligand, selection of suitable solvents, determination of reaction parameters, reaction profiles at promising reaction conditions, sensitivity analysis in continuous process operation, and adaptation [control circuit to step 2]. …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System

Künnemann

Bianga

Scheel

et al. 2019

Org. Process Res. Dev.

View full text Add to dashboard Cite

For the first time, the successful application of the homogeneously catalyzed reductive amination in a thermomorphic multiphase system (TMS) and the first reported scale-up of this reaction into a continuous process, which recovers and recycles the homogeneous catalyst in flow, is presented. Herein, the model substrate 1-decanal reacts with the secondary amine diethylamine to form the corresponding product N,N-diethyldecylamine. A thermomorphic multiphase system (TMS) is established as a recycling strategy to recover and reuse the catalyst for the continuous process. After screening different solvents for the TMS and optimizing the reaction conditions in batch mode, the recycling of the rhodium catalyst was realized in a fully automated miniplant. Parameters influencing the stability of the process were identified and optimized to develop the continuous process. The process was operated in a steady state over 90 h with yields >90% of the desired product and low catalyst leaching <1%/h.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System

Künnemann

Bianga

Scheel

et al. 2019

Org. Process Res. Dev.

View full text Add to dashboard Cite

show abstract

“…The corresponding addition of alkylsilanes to dienes is usually also Pt‐catalyzed. However, the use of proplyene carbonate (PC) as a solvent has been shown to serve as an organocatalyst in this transformation . By successful synthesis of the corresponding silyl ether, the product was effectively decanted from the PC phase and the PC phase was recycled.…”

Section: C5 Moleculesmentioning

confidence: 99%

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

et al. 2018

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Copper-Catalyzed Markovnikov Selective 3,4-Hydrosilylation of 2-Substituted 1,3-Dienes

Wang

et al. 2022

Org. Lett.

View full text Add to dashboard Cite

A copper-catalyzed regioselective Markovnikov 3,4-hydrosilylation of 2-substituted 1,3-dienes has been accomplished. A wide range of 2-substituted 1,3-dienes and trihydrosilanes are compatible under the optimal conditions. The bisphosphine ligand with a rigid backbone provides the Markovnikov 3,4-hydrosilylation product in better yield and selectivity. Besides, the synthetic utilities of the allylsilanes also were demonstrated by their flexible derivatizations.

show abstract

Specific Polar Solvents as Organocatalysts for the Hydrosilylation of Isoprene

Abstract: Isoprene was hydrosilylated in the absence of transition metals by using specific organic solvents as both reaction media and organocatalysts. A highly selective reaction with successful catalyst recycling could be performed by using propylene carbonate as the reaction medium.

Cited by 4 publications

References 18 publications

Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System

Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System

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

Copper-Catalyzed Markovnikov Selective 3,4-Hydrosilylation of 2-Substituted 1,3-Dienes

Contact Info

Product

Resources

About