Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Goanvic, Lucas Le; Ternel, Jérémy; Couturier, Jean‐Luc; Dubois, Jean‐Luc; Carpentier, Jean‐François

doi:10.3390/catal8010021

Cited by 9 publications

(6 citation statements)

References 28 publications

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“…The same trend was also observed in the case of Rh-based catalysts in previous studies carried in our lab [20]. On the other hand, very poor performances were observed with Zhang's tetraphosphine [21].22…”

Section: Ligandssupporting

confidence: 81%

Ruthenium-catalyzed hydroformylation of the functional unsaturated fatty nitrile 10-undecenitrile

Goanvic

Couturier

Dubois

et al. 2016

Journal of Molecular Catalysis A: Chemical

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The hydroformylation of 10-undecenitrile (1), a route towards polyamide-12, has been studied using Ru-diphosphite catalysts. The reactions proceeded effectively by in situ combination of chloro precursors such as RuCl 2 (PPh 3) 3 and RuCl 2 (DMSO) 4 with Biphephos. High productivities (TON up to 15,000 mol(aldehyde).mol(Ru) −1) were achieved by carrying the reactions at low catalyst loading ([1] 0 /[Ru] = 20,000), at 120 °C in toluene or acetonitrile under 20 bars CO/H 2 (1:1), with 20 equiv of Biphephos vs. Ru. Up to 75% chemoselectivity for the aldehydes and very high regioselectivities for the linear aldehyde (l/b = 99:1) were reached under such optimized conditions. Lower loadings of Biphephos (down to 2.5 equiv. vs. Ru) did not affect the chemo-and regioselectivities but the activity. The Ru-Biphephos combinations showed a non-optimized hydroformylation TOF HF of ca. 2-7 min −1 , that is ca. 1-2 order of magnitude lower than that of analogous Rh-based systems (TOF HF = ca. 80 min −1). These Ru-Biphephos systems are, however, incapable, under the conditions suitable for selective hydroformylation, to promote isomerization of internal olefins, and hence to achieve a tandem isomerization-hydroformylation process.

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Section: Ligandssupporting

confidence: 81%

Ruthenium-catalyzed hydroformylation of the functional unsaturated fatty nitrile 10-undecenitrile

Goanvic

Couturier

Dubois

et al. 2016

Journal of Molecular Catalysis A: Chemical

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“…Furthermore, comparison with state of the art Ru homogeneous catalysts is given in Table S31.1, where both the RuCl 2 (PPh 3 ) 3 biphenphos and the Ru 3 (CO) 12 -imidazoyl-substituted monophosphine system showed remarkable activities [TOF 360 and 2040 h −1 and 15 000 and 800 TON, respectively, albeit with other substrates (undec-10-enenitrile and 1-octene)]. 63,64 However, these catalytic systems required the use of complex compounds with intricate synthesis steps, leading to very expensive ligands and were operated under different reaction conditions (higher pressures and the use of co-additives) or using dissimilar substrates. Considering heterogeneous Ru catalysts, the Ru@NC catalysts used herein exhibit markedly higher activity than that of previously reported catalysts (see Table S31.2 for state of the art catalysts), accompanied by a noteworthy superior linear to branch regioselectivity.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Active and Regioselective Ru Single-Site Heterogeneous Catalysts for Alpha-Olefin Hydroformylation

et al. 2022

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A heterogeneous ruthenium catalyst consisting of isolated single atoms and disordered clusters stabilized in a N-doped carbon matrix has been synthesized with very good activity and remarkable regioselectivity in the hydroformylation of 1-hexene. The role of the nitrogen heteroatoms has been probed essential to increase the catalyst stability and activity, enabling the stabilization of Ru(II)–N sites according to X-ray photoelectron spectroscopy (XPS) and XANES. Intrinsic size-dependent activity of Ru species of different atomicity has been extracted, correlating the observed reaction rate and the particle size distribution determined by means of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, permitting the identification of single-atom sites as the most active ones. This catalyst appears as a promising alternative with respect to its heterogeneous counterparts, paving the way for designing improved Ru heterogeneous catalysts.

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“…Olefins containing the –CN group are important functionalized alkenes. Scientists have tried hard to regulate and control the regioselectivity of the catalytic hydroformylation of olefins containing the –CN functional group [ 24 , 25 , 26 ]. It is well-known that the control addition of two HCN to a single butadiene is still the most effective industrial process to synthesize adiponitrile today.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Rh/B–TNTs as a Recyclable Catalyst for Hydroformylation of Olefin Containing –CN Functional Group

Liu

Chen

et al. 2018

Nanomaterials

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The TiO2-based nanotubes (TNTs, B–TNTs) of different surface acidities and their supported Rh catalysts were designed and synthesized. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), tempera–ture–programmed desorption of ammonia (NH3–TPD), atomic emission spectrometer (ICP), and Brunauer–Emmett–Tellerv (BET) surface-area analyzers. Images of SEM and TEM showed that the boron-decorated TiO2 nanotubes (B–TNTs) had a perfect multiwalled tubular structure; their length was up to hundreds of nanometers and inner diameter was about 7 nm. The results of NH3-TPD analyses showed that B–TNTs had a stronger acid site compared with TNTs. For Rh/TNTs and Rh/B–TNTs, Rh nanoparticles highly dispersed on B–TNTs were about 2.79 nm in average diameter and much smaller than those on TNTs, which were about 4.94 nm. The catalytic performances of catalysts for the hydroformylation of 2-methyl-3-butennitrile (2M3BN) were also evaluated, and results showed that the existence of B in Rh/B–TNTs had a great influence on the catalytic performance of the catalysts. The Rh/B–TNTs displayed higher catalytic activity, selectivity for aldehydes, and stability than the Rh/TNTs.

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Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Cited by 9 publications

References 28 publications

Ruthenium-catalyzed hydroformylation of the functional unsaturated fatty nitrile 10-undecenitrile

Ruthenium-catalyzed hydroformylation of the functional unsaturated fatty nitrile 10-undecenitrile

Active and Regioselective Ru Single-Site Heterogeneous Catalysts for Alpha-Olefin Hydroformylation

Synthesis and Characterization of Rh/B–TNTs as a Recyclable Catalyst for Hydroformylation of Olefin Containing –CN Functional Group

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