Behavior of Amine in Rhodium Complex–Tertiary Amine Catalyst System Active for Hydrogenation of Aldehyde under Oxo Reaction Conditions

Mizoroki, Tsutomu; Kioka, Mamoru; Suzuki, Motohiro; Sakatani, Shiro; Okumura, Atsushi; Maruya, Ken‐ichi

doi:10.1246/bcsj.57.577

Cited by 29 publications

(11 citation statements)

References 5 publications

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“…This represents the first one‐step synthesis of phenpyramine (Milverine), an important antispasmodic agent. Previously this was not possible because the reduction of the intermediate aldehyde is promoted by the coupling partner 23…”

Section: Resultsmentioning

confidence: 99%

Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals

Ahmed

Buch

Routaboul

et al. 2007

Chemistry A European J

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Starting from [{Rh(cod)Cl}(2)] and 1,3-dimesitylimidazole-2-ylidenes the novel [RhCl(cod)(carbene)] complexes 1-5 have been synthesized, characterized, and tested in the hydroaminomethylation of aromatic olefins. The influence of different ligands and reaction parameters on the catalytic activity was investigated in detail applying 1,1-diphenylethylene and piperidine as a model system. The scope and limitations of the novel catalysts is shown in the preparation of 16 biologically active 1-amino-3,3-diarylpropenes. In general, high chemo- and regioselectivity as well as good yields of the desired products were achieved.

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Section: Resultsmentioning

confidence: 99%

Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals

Ahmed

Buch

Routaboul

et al. 2007

Chemistry A European J

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“…Upon increasing the amount of NR 3 , the equilibriums are displaced from hydroformylating Rh‐carbonyl complexes toward hydrogenating amino‐Rh complexes. [ 24 ]…”

Section: Resultsmentioning

confidence: 99%

“…Upon increasing the amount of NR 3 , the equilibriums are displaced from hydroformylating Rh-carbonyl complexes toward hydrogenating amino-Rh complexes. [24] Once the one-pot two-step process was validated at the laboratory-scale, we sought to develop the process at the kg-scale using a 5 L reactor. In this context, we first replicated the HHM conditions on larger quantities.…”

Section: Controlled Hydroxymethylation Of Vhosomentioning

confidence: 99%

One‐Pot Two‐Step Synthesis of Hydroxymethylated Unsaturated VHOSO and Its Application to the Synthesis of Biobased Polyurethanes

Cousin

Quienne

Pinaud

et al. 2020

Euro J Lipid Sci & Tech

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A one-pot two-step procedure is developed to catalytically convert very high-oleic sunflower oil (VHOSO) into hydroxymethylated unsaturated derivatives featuring both primary alcohols and carbon-carbon double bonds. The degree of functionalization in alcohols and C═C double bonds can be accurately controlled affording low and high substituted hydroxymethylated VHOSO. The key point to achieve such control is to partly hydroformylate the C═C bonds at 80°C and to subsequently reduce the reaction temperature to 20°C to selectively reduce the aldehydes, while keeping a high CO/H 2 pressure. Step-growth polymerization of highly substituted hydroxymethylated VHOSO with cyclohexyl isocyanate or 4,4ʹ-methylenebis(cyclohexyl isocyanate) furnishes biobased polyurethanes with improved thermal stability compared to similar polyurethanes synthesized from castor oil. Practical Applications: This study highlights the implementation of triglycerides featuring both C═C double bonds and hydroxymethyl groups. The synthesis proceeds through a one-pot two-steps procedure that consists of a hydroformylation reaction at 80°C followed by a hydrogenation reaction carried out at room temperature. This simple synthetic procedure is of major interest in a context of an industrial-environmental approach. The high reactivity of the obtained primary alcohols allows the synthesis of bio-PUs, displaying untouched C═C double bonds, which could be further functionalized. This finding is of importance as the obtained bio-PUs can be used in many industrial areas such as foams, elastomers, thermoplastics, thermosets, adhesives, coatings, sealants and fibers.

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“…The process in a one-step reaction with a single catalyst is the best alternative, owing to the reduction in the amount of the catalyst, the reaction time, and the overall cost. In this context, one of the best systems is a Rh-catalyst associated with tertiary amines in the presence of CO/H 2 [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 ]. In this publication, we report the HHM of isosorbide diallyl ether using this catalytic system.…”

Section: Introductionmentioning

confidence: 99%

Reductive Hydroformylation of Isosorbide Diallyl Ether

et al. 2021

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Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.

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Behavior of Amine in Rhodium Complex–Tertiary Amine Catalyst System Active for Hydrogenation of Aldehyde under Oxo Reaction Conditions

Abstract: The title reaction was investigated to elucidate the reported disagreements on the kinetics. The concentration and the coordination stability of amine were found to affect the optimum pressure of carbon monoxide and the kinetics, and were suggested to control the reaction mechanism.

Cited by 29 publications

References 5 publications

Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals

Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals

One‐Pot Two‐Step Synthesis of Hydroxymethylated Unsaturated VHOSO and Its Application to the Synthesis of Biobased Polyurethanes

Reductive Hydroformylation of Isosorbide Diallyl Ether

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