Two‐Phase Catalysis: A Strategy for Avoiding Consecutive Reactions as Exemplified in the Telomerization of Butadiene and Ammonia

Prinz, Thomas; Keim, Wilhelm; Drießen‐Hölscher, Birgit

doi:10.1002/anie.199617081

Cited by 77 publications

(34 citation statements)

References 10 publications

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“…We have shown that these consecutive reactions can be avoided by using the two-phase method, [4] which allows the selective production of the primary amines 1 and 2. The reaction takes place in an aqueous catalyst phase and the primary products are extracted in situ by a second organic phase (e.g.…”

Section: Introductionmentioning

confidence: 99%

Biphasic Catalyzed Telomerization of Butadiene and Ammonia: Kinetics and New Ligands for Regioselective Reactions

Prinz

Drießen‐Hölscher

1999

Chem. Eur. J.

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The kinetics of the palladiumcatalyzed biphasic telomerization of butadiene and ammonia by means of in situ catalysts consisting of phosphane palladium complexes were investigated at 80 8C. The effects of ligand, catalyst, and ammonia concentrations were studied. The rate of product formation as well as the regioselectivity of the reaction was found to depend greatly on ligand and catalyst concentration. A model for the reaction mechanism was deduced from these results, explaining the regioselectivities obtained. The regioselectivity could be strongly influenced by the ligand. We synthesized new water-soluble phosphanes with special p-acceptor/s-donor properties for use in the telomerization reaction. TPPTS as a ligand gave the terminal octadienylamine with a regioselectivity of 50 %, whilst a TPPTS derivative with three methoxy groups in ortho positions led to a regioselectivity of 94 %. This corroborated the importance of ligand properties in this reaction.

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Section: Introductionmentioning

confidence: 99%

Biphasic Catalyzed Telomerization of Butadiene and Ammonia: Kinetics and New Ligands for Regioselective Reactions

Prinz

Drießen‐Hölscher

1999

Chem. Eur. J.

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“…Moreover, in these two-phase systems it is possible to extract the primary products during the reaction and thus modulate the product selectivity 5 . Amongst the "mobile" phases employed for the immobilization of transitionmetal catalyst precursors 3,4,6,7 molten salts are attracting increasing and continuous interest amongst academic and industrial chemists 8 .…”

Section: Introductionmentioning

confidence: 99%

Pd(II)-dissolved in ionic liquids: a recyclable catalytic system for the selective biphasic hydrogenation of dienes to monoenes

Dupont¹,

Suarez²,

Umpierre³

et al. 2000

J. Braz. Chem. Soc.

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Bis-acetilacetonato de paládio dissolvido no líquido iônico tetrafluoroborato de 1-n-butil-3-metilimidazólio catalisa de forma seletiva a hidrogenação de dienos conjugados e não-conjugados (funcionalizados ou não) às suas respectivas mono-olefinas. O sistema não requer o uso de cosolventes orgânicos, sendo os produtos da reação separados por simples decantação ou destilação. A fase iônica pode ser reutilizada até 15 vezes sem perdas significativas na sua atividade catalítica e seletividade.Palladium acetylacetonate dissolved in 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid catalyses the selective two-phase hydrogenation of conjugated and non-conjugated (functionalized and non-functionalized) dienes into the respective monoenes. The system does not require the use of organic solvents, the products are removed by simple decantation or distillation and the recovered ionic catalytic solution can be reused several times without any significant changes in its catalytic activity and selectivity.

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“…[11] Unfortunately, the corresponding coupling products have to be cleaved after the reaction, which leads to unwanted side products. [12] Hence, the use of ammonia as an N-nucleophile is still by far the most desired approach [13] because of its inherent atom economy, and the low cost and availability of ammonia. [14] In 2006, Hartwig and Shen [15] published the first selective palladium-catalyzed monoarylation of ammonia employing the bulky Josiphos bisphosphine 1 as ancillary ligand (Scheme 1).…”

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A General Palladium‐Catalyzed Amination of Aryl Halides with Ammonia

Schulz

Torborg

Enthaler

et al. 2009

Chemistry A European J

159

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A new robust palladium/phosphine catalyst system for the selective monoarylation of ammonia with different aryl bromides and chlorides has been developed. The active catalyst is formed in situ from [Pd(OAc)(2)] and air- and moisture-stable phosphines as easy-to-handle pre-catalysts. The productivity of the catalyst system is comparable to that of competitive Pd/phosphine systems; full conversion is achieved with most substrates with 1-2 mol % of Pd source and a fourfold excess of ligand (L).

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Two‐Phase Catalysis: A Strategy for Avoiding Consecutive Reactions as Exemplified in the Telomerization of Butadiene and Ammonia

Cited by 77 publications

References 10 publications

Biphasic Catalyzed Telomerization of Butadiene and Ammonia: Kinetics and New Ligands for Regioselective Reactions

Biphasic Catalyzed Telomerization of Butadiene and Ammonia: Kinetics and New Ligands for Regioselective Reactions

Pd(II)-dissolved in ionic liquids: a recyclable catalytic system for the selective biphasic hydrogenation of dienes to monoenes

A General Palladium‐Catalyzed Amination of Aryl Halides with Ammonia

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