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Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins.

ABSTRACT: Single-atom Rh catalysts present superior activity relative to homogeneous catalyst in olefins hydroformylation, yet with limited success in regioselectivity control. In the present work, we develop a phosphorus coordinated Rh₁ single-atom catalyst with nanodiamond as support. Benefiting from this unique structure, the catalyst exhibits excellent activity and regioselectivity in hydroformylation of arylethylenes with wide substrate generality, i.e., with high conversion (>99%) and high regioselectivity (>90%), which is comparable with the homogeneous counterparts. The coordination interaction between Rh₁ and surface phosphorus species is clarified by ³¹P solid-state NMR and X-ray absorption spectroscopy (XAS). Rh single atoms are firmly anchored over nanodiamond through Rh-P bonds, guaranteeing good stability in the hydroformation of styrene even after six runs. Finally, by using this catalyst, two kinds of pharmaceutical molecules, Ibuprofen and Fendiline, are synthesized efficiently with high yields, demonstrating a new prospect of single-atom catalyst in pharmaceutical synthesis.

SUBMITTER: Gao P

PROVIDER: S-EPMC8339002 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst.

Project description:Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h-1 among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.

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Enhancing the stability of the Rh/ZnO catalyst by the growth of ZIF-8 for the hydroformylation of higher olefins.

Project description:Hydroformylation of olefins is one of the most important industrial processes for aldehyde production. Therein, the leaching of active metals for heterogeneous catalysts is an important issue in the hydroformylation reaction, particularly for higher olefins to produce higher alcohols. Here, different Rh/ZnO catalysts with diverse ZnO as a support were investigated and a home-made ZnO50 support was selected to prepare the Rh/ZnO50@ZIF-8 core-shell structure catalyst, which was synthesized by the growth of ZIF-8 with ZnO50 as the sacrificed template to afford Zn source. Compared with the Rh/ZnO50 catalyst, the Rh/ZnO50@ZIF-8 catalyst demonstrated a better cyclic stability in the hydroformylation of 1-dodecene. Combining the experiment and characterization results, it was concluded that the ZIF-8 shell on the Rh/ZnO50 catalyst effectively prevented the leaching of metal Rh into the reaction solution. Moreover, the Rh/ZnO50@ZIF-8 catalyst exhibited good universality for other higher olefins. This work provides a useful guideline for immobilizing the active species in heterogeneous catalysts for the hydroformylation reaction.

| S-EPMC9056783 | biostudies-literature

Regioselective hydroformylation of allylic alcohols.

Project description:A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.

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

Project description:The TiO?-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 (NH??TPD), atomic emission spectrometer (ICP), and Brunauer?Emmett?Tellerv (BET) surface-area analyzers. Images of SEM and TEM showed that the boron-decorated TiO? 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 NH?-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.

| S-EPMC6215287 | biostudies-literature

Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles.

Project description:We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress ?-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.

| S-EPMC5872806 | biostudies-literature

Rh-Catalyzed Hydroformylation-Initiated Bicyclization: Construction of Azabicyclic Systems.

Project description:Here, we describe the recent progress toward construction of 1-azabicyclic structures using a domino hydroformylation double cyclization strategy of an amide bearing the trisubstituted alkene functionality. The method provides a rapid and atom-economic access to alkaloid structures under mild conditions, especially for quinolizidine and pyrrolidine-fused azepane skeletons with yields up to 82% and good diastereoselectivity. Subsequent oxidative cleavage conditions are developed for the synthesis of Dendrobatid alkaloid epi-epiquinamide.

| S-EPMC7045571 | biostudies-literature

O-coordinated W-Mo dual-atom catalyst for pH-universal electrocatalytic hydrogen evolution.

Project description:Single-atom catalysts (SACs) maximize the utility efficiency of metal atoms and offer great potential for hydrogen evolution reaction (HER). Bimetal atom catalysts are an appealing strategy in virtue of the synergistic interaction of neighboring metal atoms, which can further improve the intrinsic HER activity beyond SACs. However, the rational design of these systems remains conceptually challenging and requires in-depth research both experimentally and theoretically. Here, we develop a dual-atom catalyst (DAC) consisting of O-coordinated W-Mo heterodimer embedded in N-doped graphene (W1Mo1-NG), which is synthesized by controllable self-assembly and nitridation processes. In W1Mo1-NG, the O-bridged W-Mo atoms are anchored in NG vacancies through oxygen atoms with W?O?Mo?O?C configuration, resulting in stable and finely distribution. The W1Mo1-NG DAC enables Pt-like activity and ultrahigh stability for HER in pH-universal electrolyte. The electron delocalization of W?O?Mo?O?C configuration provides optimal adsorption strength of H and boosts the HER kinetics, thereby notably promoting the intrinsic activity.

| S-EPMC7274769 | biostudies-literature

Computational Study of Rh-Catalyzed Carboacylation of Olefins: Ligand-Promoted Rhodacycle Isomerization Enables Regioselective C-C Bond Functionalization of Benzocyclobutenones.

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| S-EPMC4878673 | biostudies-literature

Cofactor Controlled Encapsulation of a Rhodium Hydroformylation Catalyst.

Project description:Supramolecular approaches in transition-metal catalysis, including catalyst encapsulation, have attracted considerable attention. Compared to enzymes, supramolecular catalysts in general are less complex. Enzyme activity is often controlled by the use of smaller cofactor molecules, which is important in order to control reactivity in complex mixtures of molecules. Interested in increasing complexity and allowing control over supramolecular catalyst formation in response to external stimuli, we designed a catalytic system that only forms an efficient supramolecular complex when a small cofactor molecule is added to the solution. This in turn affects both the activity and selectivity when applied in a hydroformylation reaction. This contribution shows that catalyst encapsulation can be controlled by the addition of a cofactor, which affects crucial catalyst properties.

| S-EPMC6563692 | biostudies-literature

Organic chemistry. Rh-catalyzed C-C bond cleavage by transfer hydroformylation.

Project description:The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rhodium (Xantphos)(benzoate) catalyst activates aldehyde carbon-hydrogen (C-H) bonds with high chemoselectivity to trigger carbon-carbon (C-C) bond cleavage and generate olefins at low loadings (0.3 to 2 mole percent) and temperatures (22° to 80°C). This mild protocol can be applied to various natural products and was used to achieve a three-step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton shuttle to enable transfer hydroformylation.

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