Efficient hydroaminomethylation of olefins catalyzed by Rh-complex ligated by P,O-hybrid ligand with chelating effect

Chen, Xiao‐Chao; Lan, Tian; Zhao, Kai‐Chun; Guo, Lin; Lu, Yong; Liu, Ye

doi:10.1016/j.jcat.2022.05.010

Cited by 3 publications

(4 citation statements)

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“…As can be imagined, when the bulkier solid main-chain polymer NHC–Rh ( 6b ) has many similar repeating units, the hindrance around the metal center will be further enhanced. Compared with the carefully designed bulky ligands in previous reports, 22–26 the constrained hindrance caused by the supramolecular coordination assembly may be further enforced by entangling the assembly main chains in the solid state, leading to excellent selectivity in HAM. In addition to the aforementioned role of the π-conjugation system of NHCs and constrained assembly hindrance, the counter-ions and ancillary ligands of the solid catalysts were also found to slightly affect the activity and selectivity.…”

Section: Resultsmentioning

confidence: 94%

“…8,11,12 Therefore, various efforts have thus been devoted to the design of bi-functional catalytic systems. 20–27 By using 2-fluoro-4-methylbenzoic acid as a co-catalyst, Abolhasani and co-workers increased the reactivity of Rh/4,5-bis(diphenylphosphino)-9,9-dimethyl-xanthene by 70-fold in HAM. 20 Chen's group synthesized water-soluble diphosphine ligands and applied them in Rh-catalyzed HAM of vinylarenes using anilines in water with good branch selectivity.…”

Section: Introductionmentioning

confidence: 99%

“…21 Despite these advances, various stoichiometric additives still have to be added to achieve satisfactory yields and regioselectivity. 13–27…”

Section: Introductionmentioning

confidence: 99%

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Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

et al. 2023

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Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

et al. 2023

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“…While the idea of converting small molecules into larger and more complex ones seems appealing, it often requires reactions occurring over different active sites (e.g., acylation of aldehydes on Lewis acid and base sites, hydrogenation–hydroformylation over central nitrogen in tertiary amine on metal sites, and alkene metathesis on redox and acid sites). − Even so, tandem (cascade or domino) reactions have proven effective in facilitating such complex transformations in a single step by utilizing multifunctional catalysts. − Examples of such reactions include tandem dehydrogenation and olefin cross-metathesis, − tandem ammonia borane dehydrogenation and hydrogenation of amines, and tandem hydrogenation of nitroarenes . Tandem reactions are further attractive as they promote process intensification, reducing capital and operational costs by consolidating multiple reaction steps in a single reactor. − As such, tandem hydrogenation of carbon dioxide (CO 2 ) with “green H 2 ”, which couples two major reactions: CH 3 OH synthesis reaction and CH 3 OH to hydrocarbons conversion (MTH), to produce HC has emerged as an attractive route to advance toward a sustainable and carbon-neutral circular economy. ,− …”

Section: Introductionmentioning

confidence: 99%

Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In₂O₃/HZSM-5 Tandem CO₂ Hydrogenation Catalyst

Mahnaz,

Mangalindan,

Dharmalingam

et al. 2024

ACS Sustainable Chem. Eng.

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Identifying the descriptors for the synergistic catalytic activity of bifunctional oxide-zeolite catalysts constitutes a formidable challenge in realizing the potential of tandem hydrogenation of CO 2 to hydrocarbons (HC) for sustainable fuel production. Herein, we combined CH 3 OH synthesis from CO 2 and H 2 on In 2 O 3 and methanol-to-hydrocarbons (MTH) conversion on HZSM-5 and discerned the descriptors by leveraging the distance-dependent reactivity of bifunctional In 2 O 3 and HZSM-5 admixtures. We modulated the distance between redox sites of In 2 O 3 and acid sites of HZSM-5 from milliscale (∼10 mm) to microscale (∼300 μm) and observed a 3-fold increase in space-time yield of HC and CH 3 OH (7.5 × 10 −5 mol C g cat −1 min −1 and 2.5 × 10 −5 mol C g cat −1 min −1 , respectively), due to a 10-fold increased rate of CH 3 OH advection (1.43 and 0.143 s −1 at microscale and milliscale, respectively) from redox to acid sites. Intriguingly, despite the potential of a three-order-of-magnitude enhanced CH 3 OH transfer at a nanoscale distance (∼300 nm), the sole product formed was CH 4 . Our reactivity data combined with Raman, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) revealed the occurrence of solid-state-ion-exchange (SSIE) between acid sites and In δ+ ions, likely forming In 2 O moieties, inhibiting C−C coupling and promoting CH 4 formation through CH 3 OH hydrodeoxygenation (HDO). Density functional theory (DFT) calculations further revealed that CH 3 OH adsorption on the In 2 O moiety with preadsorbed and dissociated H 2 forming an H−In−OH−In moiety is the likely reaction mechanism, with the kinetically relevant step appearing to be the hydrogenation of the methyl species. Overall, our study revealed that efficient CH 3 OH transfer and prevention of ion exchange are the key descriptors in achieving catalytic synergy in bifunctional In 2 O 3 /HZSM-5 systems.

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A Chemoenzymatic Hydroaminomethylation Strategy for the Selective Synthesis of Linear Primary Amines from Olefins by Sequential and Tandem Processes

Manske,

Nicolai,

Bloomer

et al. 2024

ACS Catal.

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Methods that form amines from feedstock chemicals are an important component of industrial chemistry. Many methods for the synthesis of amines yield mixtures of primary, secondary, and tertiary amines, necessitating costly downstream separations. We present a chemoenzymatic approach to hydroaminomethylation that addresses these challenges by combining hydroformylation catalyzed by a phosphine-bound rhodium complex with enzymatic transamination catalyzed by an ω-transaminase from Vibrio fluvialis (VfTA). This sequential chemoenzymatic hydroaminomethylation reaction converts olefins to linear primary amines with high regioselectivity and chemoselectivity for the linear primary amine, and we demonstrate that this process occurs with a series of olefins with varying structures. Furthermore, we report progress toward a tandem process that incorporates a biocatalytic cascade for recycling an intermediate amine donor, which is required for the transaminase enzyme to use an ammonium salt as the terminal nitrogen source. This study illustrates the potential to combine chemo- and biocatalytic reactions to produce valuable materials from readily available feedstocks in both tandem and sequential processes, with selectivities that have not been achieved with transition-metal catalysts.

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Efficient hydroaminomethylation of olefins catalyzed by Rh-complex ligated by P,O-hybrid ligand with chelating effect

Cited by 3 publications

References 53 publications

Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In₂O₃/HZSM-5 Tandem CO₂ Hydrogenation Catalyst

A Chemoenzymatic Hydroaminomethylation Strategy for the Selective Synthesis of Linear Primary Amines from Olefins by Sequential and Tandem Processes

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Efficient hydroaminomethylation of olefins catalyzed by Rh-complex ligated by P,O-hybrid ligand with chelating effect

Cited by 3 publications

References 53 publications

Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In2O3/HZSM-5 Tandem CO2 Hydrogenation Catalyst

A Chemoenzymatic Hydroaminomethylation Strategy for the Selective Synthesis of Linear Primary Amines from Olefins by Sequential and Tandem Processes

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Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In₂O₃/HZSM-5 Tandem CO₂ Hydrogenation Catalyst