Hydrogenation Of Imines Research Articles

The Proton of Alcohols as Hydrogen Source in Diboron-Mediated Nickel-Catalyzed Asymmetric Transfer Hydrogenation of Cyclic N-Sulfonyl Imines.

The proton of alcohols as the sole hydrogen source in diboron-mediated nickel-catalyzed asymmetric transfer hydrogenation of cyclic N-sulfonyl imines has been developed, providing the chiral cyclic sulfamidates in excellent enantioselectivities. The mechanistic investigations suggested that the proton of alcohols could be activated by tetrahydroxydiboron to form active nickel hydride species.

Iridium-Catalyzed Asymmetric Hydrogenation of Dialkyl Imines

Iridium-Catalyzed Asymmetric Hydrogenation of Dialkyl Imines

Self-Powered and Self-Healable Extraocular-Muscle-Like Actuator Based on Dielectric Elastomer Actuator and Triboelectric Nanogenerator.

Although dielectric elastomer actuators (DEAs) are promising artificial muscles for use as visual prostheses in patients with oculomotor nerve palsy (ONP), high driving voltage coupled with vulnerable compliant electrodes limits their safe long-term service. Herein, a self-healable polydimethylsiloxane compliant electrode based on reversible imine bonds and hydrogen bonds is prepared and coated on an acrylic ester film to develop a self-healable DEA (SDEA), followed by actuation with a high-output triboelectric nanogenerator (TENG) to construct a self-powered DEA (TENG-SDEA). Under 135.9kVmm-1 , the SDEA exhibits an elevated actuated strain of 50.6%, comparable to the actuation under DC power. Moreover, the mechanically damaged TENG-SDEA displays a self-healing efficiency of over 90% for 10 cycles. The TENG ensures the safe using of TENG-SDEAs and an extraocular-muscle-like actuator with oriented motion ability integrated by several TENG-SDEAs is constructed. Additionally, the SDEA is directly used as a flexible capacitive sensor for real-time monitoring of the patient's muscle movement. Accordingly, a medical aid system based on a conjunction of the extraocular-muscle-like actuator and a flexible capacitive sensor is manufactured to help the patients suffering from ONP with physical rehabilitation and treatment.

Activity enhancement of Ru/CeO2 for N-alkylation of amines with alcohols through tailoring metal-support interaction

Efficient and selective N-alkylation of amines with alcohols via transfer hydrogenation is of great significance but extremely challenging. Here, we report the production of N–benzylaniline (BZA) from benzyl alcohol and aniline over various fine-shaped Ru/CeO2 catalysts. The Ru/CeO2–R (rod) catalyst exhibits the highest catalytic activity among all catalysts, in which the yield of BZA reaches up to 88% with complete conversion, significantly higher than that of Ru/CeO2-C (cube, 52%) and Ru/CeO2-O (octahedron, 32%). Extensive experimental investigations disclose that Ru nanoparticles with a metallic state promote the dehydrogenation of the hydroxyl group and hydrogenation of imines, while the CeO2–R with rich oxygen vacancies facilitates the adsorption and activation of reactants. Furthermore, kinetic studies and time-resolved operando dual-beam Fourier transform infrared spectroscopy analysis confirms the transfer hydrogenation pathway, in which the benzyl alcohol is firstly dehydrogenated to benzaldehyde, followed by spontaneously reacting with aniline, and finally transforms into the N-benzylaniline rapidly.

Role of alkaline-earth metal in catalysed imine hydrogenations

Alkaline-earth metal (Ae) catalysts have been recently developed for challenging imine and alkene hydrogenation at moderate reaction conditions, providing a sustainable alternative to transition metal catalysis. The understanding of catalytic hydrogenations mediated by group 2 metals is underdeveloped and mechanistic studies are scarce from experimental and computational sides. Herein, we examine the role of the metal on the catalytic hydrogenation of imines by Ae[N(SiMe3)2]2 (Ae = Mg, Ca, Sr, Ba) using state-of-the-art computational techniques. Trends in energy barriers and turnover frequencies agree remarkably well with the experimentally observed increase in catalytic activity upon descending group 2 (Mg ≪ Ca < Sr < Ba). Structural and chemical bonding differences in the key intermediates were found to be the main driving force behind the enhanced reactivity of heavier Ae catalysts. More specifically, the N-Ae-H^ bond angle is drastically reduced in the Ca, Sr, and Ba catalytic species driven by the participation of the d-orbitals in the chemical bonding. The activation strain model reveals that these catalytic reactions are strain controlled and the higher activation barriers for the Mg catalyst originates from unfavourable bond angles in the Mg hydride species featuring linear structures and a more covalent metal-hydride bond. Further decomposition of the interaction energy reveals that stronger repulsive interactions destabilize the Mg species, indicating that the steric congestion due to the small Mg centre impedes reaction kinetics. Overall, the different aspects to be considered in the Ae catalyst design for imine hydrogenations are the strength and flexibility of the Ae-H bond, the bond ionicity, the N-Ae-H^ angle and the strength of the noncovalent interactions in the TOF-determining intermediate.

Benzimidazol-2-ylidene ruthenium complexes for C-N bond formation through alcohol dehydrogenation.

A low temperature hydrogen borrowing approach to generate secondary amines using benzimidazole-based N-heterocyclic carbene (BNHC) ruthenium complexes is reported. A series of the piano-stool complexes of the type [(η6-p-cymene)(BNHC)RuCl2] (1a-g) were synthesized via one-pot reaction of the NHC salt precursor, Ag2O, and [RuCl2(p-cymene)]2 and characterized using conventional spectroscopic techniques. The geometry of two precursors, [(η6-p-cymene)(Me4BnMe2BNHCCH2OxMe)RuCl2] (1f) and [(η6-p-cymene)(Me5BnMe2BNHCCH2OxMe)RuCl2] (1g), was studied by single crystal X-ray diffraction. These catalysts were found to dehydrogenate alcohols efficiently at temperatures as low as 50 °C to allow Schiff-base condensation and subsequent imine hydrogenation to afford secondary amines. Notably, this ruthenium-based procedure enables the N-alkylation of aromatic and heteroaromatic primary amines with a wide range of primary alcohols in excellent yields of up to 98%. The present methodology is green and water is liberated as the sole byproduct.

The Acquisition of Primary Amines from Alcohols through Reductive Amination over Heterogeneous Catalysts

The synthesis of primary amines via the reductive amination of alcohols involves a hydrogen-borrowing or hydrogen-transfer mechanism, which consists of three main steps: alcohol hydroxyl dehydrogenation, carbonyl imidization, and imine hydrogenation. Heterogeneous catalysts are widely used for this reaction because of their high performance and amenability to separation and reuse. However, the efficiency of reductive amination is limited by the dehydrogenation step, which is severely affected by the competitive adsorption of NH3. We hope to improve the efficiency of reductive amination by increasing dehydrogenation efficiency. Therefore, in this overview, we introduce the research progress of alcohol reductive amination reaction catalyzed by heterogeneous metal catalysts, focusing on methods of enhancing dehydrogenation efficiency by screening the metal component and the acidity/alkalinity of the support. Finally, we propose some new strategies for the preparation of catalysts from the perspective of overcoming the competitive adsorption of NH3 and speculate on the design and synthesis of novel catalysts with high performance in the future.

Fabrication of versatile poly(xylitol sebacate)-co-poly(ethylene glycol) hydrogels through multifunctional crosslinkers and dynamic bonds for wound healing

Poly(polyol sebacate) (PPS) polymer family has been recognized as promising biomaterials for biomedical applications with their characteristics of easy production, elasticity, biodegradation, and cytocompatibility. Poly(xylitol sebacate)-co-poly(ethylene glycol) (PXS-co-PEG) has been developed to fabricate PPS-based hydrogels; however, current PXS-co-PEG hydrogels presented limited properties and functions due to the limitations of the crosslinkers and crosslinking chemistry used in the hydrogel formation. Here, we fabricate a new type of PXS-co-PEG hydrogels through the use of multifunctional crosslinkers as well as dynamic bonds. In our design, polyethyleneimine-polydopamine (PEI-PDA) macromers are utilized to crosslink aldehyde-functionalized PXS-co-PEG (APP) through imine bonds and hydrogen bonds. PEI-PDA/APP hydrogels present multiple functional properties (e.g., fluorescent, elastomeric, biodegradable, self-healing, bioadhesive, antioxidant, and antibacterial behaviors). These properties of PEI-PDA/APP hydrogels can be fine-tuned by changing the PDA grafting degrees in the PEI-PDA crosslinkers. Most importantly, PEI-PDA/APP hydrogels are considered promising wound dressings to promote tissue remodeling and prevent bacterial infection in vivo. Taken together, PEI-PDA/APP hydrogels have been demonstrated as versatile biomaterials to provide multiple tailorable properties and desirable functions to expand the utility of PPS-based hydrogels for advanced biomedical applications. Statement of significanceVarious strategies have been developed to fabricate poly(polyol sebacate) (PPS)-based hydrogels. However, current PPS-based hydrogels present limited properties and functions due to the limitations of the crosslinkers and crosslinking chemistry used in the hydrogel formation. This work describes that co-engineering crosslinkers and interfacial crosslinking is a promising approach to synthesizing a new type of poly(xylitol sebacate)-co-poly(ethylene glycol) (PXS-co-PEG) hydrogels as multifunctional hydrogels to expand the utility of PPS-based hydrogels for advanced biomedical applications. The fabricated hydrogels present multiple functional properties (e.g., fluorescent, biodegradable, elastomeric, self-healing, bioadhesive, antioxidative, and antibacterial), and these properties can be fine-tuned by the defined crosslinkers. The fabricated hydrogels are also used as promising wound dressing biomaterials to exhibit promoted tissue remodeling and prevent bacterial infection in vivo.

Divergent synthesis of chiral amines via Ni-catalyzed chemo- and enantioselective hydrogenation of alkynone imines

Divergent synthesis of chiral amines via Ni-catalyzed chemo- and enantioselective hydrogenation of alkynone imines

Dissymmetrically Substituted Diphosphines with Two Atropisomeric Axes and Their Application in Asymmetric Hydrogenation of Imines

AbstractDespite the great potential and widespread applications, the majority of diphosphine ligands used in asymmetric catalysis are C2‐symmetric and their structural modifications are often limited. Herein, we reported the design of original enantiopure dissymmetrical diphosphines, BiaxPhos, bearing two atropisomeric axes. Their original chiral architecture combined with important modularity, renders BiaxPhos ligands appealing candidates for asymmetric catalysis, as illustrated by the Ir‐BiaxPhos catalyzed asymmetric imines hydrogenation, furnishing chiral amines with excellent enantioselectivities under mild conditions. Remarkably, combined experimental mechanistic investigations and DFT calculations delineate yet unexplored mechanistic scenario implying the hydrogenation of the enamine tautomeric form instead of the classic reduction of the imine.

High activities of nickel (II) complexes containing phosphorus-nitrogen ligands in hydrogen transfer reaction of imines using formic acid as a renewable hydrogen source

The catalytic reduction of imines to obtain secondary amines is an important route in the synthesis of molecules of biological or pharmaceutical interest. A series of new nickel (II) complexes bearing phosphorous-nitrogen (P,N) or phosphorous-nitrogen-phosphorous (P,N,P) ligands were characterized and studied as catalysts in hydrogen transfer reaction of imines, using formic acid as a hydrogen source, while avoiding the use of molecular hydrogen (H2). The complexes, of general formula NiCl2(L), [Ni(L)2](CF3SO3)2 (in which L is a P,N ligand) and [NiCl(L)]Cl (in the case of a tridentate PNP ligand), were active catalysts in the imine hydrogen, with turnover frequencies (TOF) up to 373 h−1 with NiCl2L1 complex (L1 = 2-(diphenylphosphinoamino) pyridine) and N-benzylideneaniline as substrate, while a [Ni(L)2](CF3SO3)2 complex bearing the same P,N ligand achieved a slightly lower activity (TOF = 320 h−1). Catalyst recyclability was also studied, achieving near full conversion after four cycles, with a total substrate/catalyst ratio of 1000:1.

Enhancement of Knölker Iron Catalysts for Imine Hydrogenation by Predictive Catalysis: From Calculations to Selective Experiments

Enhancement of Knölker Iron Catalysts for Imine Hydrogenation by Predictive Catalysis: From Calculations to Selective Experiments

Brønsted Acid Catalysis - Controlling the Competition of Monomeric versus Dimeric Reaction Pathway Enhances Stereoselectivities.

Chiral phosphoric acids (CPA) have become a privileged catalyst type in organocatalysis, but the selection of the optimum catalyst is still challenging. So far hidden competing reaction pathways may limit the maximum stereoselectivities and the potential of prediction models. In CPA catalyzed transfer hydrogenation of imines, we identified for many systems two reaction pathways with inverse stereoselectivity, featuring as active catalyst either one CPA or a hydrogen bond bridged dimer. NMR measurements and DFT calculations revealed the dimeric intermediate and a stronger substrate activation via cooperativity. Both pathways are separable: Low temperatures and high catalysts loadings favor the dimeric pathway (ee up to -98%), while low temperatures with reduced catalyst loading favor the monomeric pathway and give significantly enhanced ee (92-99% ee; prior 68-86% at higher temperatures). Thus, a broad impact is expected on CPA catalysis regarding reaction optimization and prediction.

Asymmetric Hydrogenation of Imines Using NHC‐Phosphine Iridium Complexes

Abstractα‐Chiral amines represent a frequently observed functional group in pharmaceuticals. Here, the synthesis of such motifs (up to 91% ee) is described by asymmetric hydrogenation of imines catalyzed by NHC,P‐iridium complexes. The hydrogenation proceeded smoothly, even under balloon pressure of hydrogen atmosphere. Mechanistic experiments indicated that the reduction most likely advances by a combination of direct hydrogenation and a hydrogen transfer process using either H2 or iPrOH as the reductant, respectively.

Brønstedsäure‐Katalyse – Kontrolle der Konkurrenz zwischen monomerem und dimerem Reaktionsweg erhöht Stereoselektivität

AbstractChirale Phosphorsäuren (CPS) sind inzwischen ein bevorzugter Katalysatortyp in der Organokatalyse, jedoch bleibt die Auswahl der optimalen Katalysatorstruktur weiterhin eine Herausforderung. Zusätzlich können unbekannte konkurrierende Reaktionswege die maximale Stereoselektivität und das Potenzial von Vorhersagemodellen einschränken. Bei der CPS‐katalysierten Transferhydrierung von Iminen haben wir für viele Systeme zwei Reaktionswege mit inverser Stereoselektivität gefunden, bei denen entweder eine monomere CPS oder ein Wasserstoffbrücken‐verknüpftes Dimer als Katalysator fungiert. NMR‐Messungen und DFT‐Berechnungen offenbarten ein dimeres Intermediat mit einer stärkeren Substrataktivierung durch Kooperativitätseffekte. Beide Wege können separiert werden: Niedrige Temperaturen und hohe Katalysatoranteile begünstigen den dimeren Reaktionsweg (ee bis zu −98 %), während niedrige Temperaturen und reduzierte Katalysatoranteil den monomeren Reaktionsweg fördern und zu einem signifikant verbesserten ee führen (92–99 % ee; vorher 68–86 % bei höheren Temperaturen). Insgesamt wird eine große Auswirkung auf die CPS‐Katalyse in Bezug auf Reaktionsoptimierung und Vorhersage erwartet.

Designing New Magnesium Pincer Complexes for Catalytic Hydrogenation of Imines and N-Heteroarenes: H2 and N-H Activation by Metal-Ligand Cooperation as Key Steps.

Utilization of main-group metals as alternatives to transition metals in homogeneous catalysis has become a hot research area in recent years. However, their application in catalytic hydrogenation is less common due to the difficulty in heterolytic cleavage of the H-H bond. Employing aromatization/de-aromatization metal-ligand cooperation (MLC) highly enhances the H2 activation process, offering an efficient approach for the hydrogenation of unsaturated molecules catalyzed by main-group metals. Herein, we report a series of new magnesium pincer complexes prepared using PNNH-type pincer ligands. The complexes were characterized by NMR and X-ray single-crystal diffraction. Reversible activation of H2 and N-H bonds by MLC employing these pincer complexes was developed. Using the new magnesium complexes, homogeneously catalyzed hydrogenation of aldimines and ketimines was achieved, affording secondary amines in excellent yields. Control experiments and DFT studies reveal that a pathway involving MLC is favorable for the hydrogenation reactions. Moreover, the efficient catalysis was extended to the selective hydrogenation of quinolines and other N-heteroarenes, presenting the first example of hydrogenation of N-heteroarenes homogeneously catalyzed by early main-group metal complexes. This study provides a new strategy for hydrogenation of C═N bonds catalyzed by magnesium compounds and enriches the research of main-group metal catalysis.

Cross-linked entanglement of aldehyde and amine-functionalized nanocellulose reinforced with biomineralization to produce an all-bio-based adhesive

Today, bottom-up approaches for building high-performance adhesives remain elusive due to a lack of multi-scale modules that can satisfy the robustness, cohesion, and water resistance requirements. Therefore, the development of green and sustainable biomass adhesives is attractive but remains a challenge. In this work, we used the “take from wood, back to wood” concept, which was combined with the development of a new cellulose-based wood binder. First, dialdehyde-functionalized nanocellulose (DAC) and amine-functionalized nanocellulose (AC) were successfully prepared from microcrystalline cellulose through oxidation and grafting reactions. Second, a rigid bio-inspired mineralized cellulose framework (AC@SiO2) was constructed by using tetraethoxysilane (TEOS) as a precursor to induce the in-situ growth and deposition of SiO2 via the sol–gel method on a cellulose template. Furthermore, we demonstrated that rapid gelation could be achieved by mixing DAC and AC@SiO2 nano-colloid solutions to form a concrete-like reinforcement structure of DAC/AC@SiO2 within 15 s at room temperature. DAC was considered to be the cement (binding phase), while AC@SiO2 played the role of the reinforcement (strengthening phase). The cellulose-based entanglement network gained cohesion through imine bonds, hemiacetal bonds, hydrogen bonds, hydrophobic interactions, and entanglement between the cellulose chains, leading to enhanced and toughened bonding properties. Dry and wet shear strengths of 2.05 and 1.26 MPa were achieved for the adhesives with a solid content of 20%. This new and sustainable strategy produced a functionalized cellulose colloid with a strong and stable crosslinked entanglement network, and also achieved high bonding performance.

Spatial Decoupling of Redox Chemistry for Efficient and Highly Selective Amine Photoconversion to Imines.

Light-driven primary amine oxidation to imines integrated with H2 production presents a promising means to simultaneous production of high-value-added fine chemicals and clean fuels. Yet, the effectiveness of this strategy is generally limited by the poor charge separation of photocatalysts and uncontrolled hydrogenation of imines to secondary amines. Herein, a spatial decoupling strategy is proposed to isolate redox chemistry at distinct sites of photocatalysts, and CoP core-ZnIn2S4 shell (CoP@ZnIn2S4) coaxial nanorods are assembled as the proof-of-concept photocatalyst. Directional and ultrafast carrier separation occurs between the CoP core and the ZnIn2S4 shell, as confirmed by in situ X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and transient absorption spectroscopy analyses. Toward the photoconversion of model substrate benzylamine to N-benzylbenzaldimine, CoP@ZnIn2S4 exhibits a 48-time higher production rate and >99% selectivity when compared to ZnIn2S4 (ca. 20% selectivity), and the detailed reaction mechanism has been verified by in situ diffuse reflectance infrared Fourier transform spectroscopy.

Structure-Reactivity Relationships in Borane-Based FLP-Catalyzed Hydrogenations, Dehydrogenations, and Cycloisomerizations.

ConspectusThe activation of molecular hydrogen by main-group element catalysts is an extremely important approach to metal-free hydrogenations. These so-called frustrated Lewis pairs advanced within a short period of time to become an alternative to transition metal catalysis. However, deep understanding of the structure-reactivity relationship is far less developed compared to that of transition metal complexes, although it is paramount for advancing frustrated Lewis pair chemistry.In this Account, we provide detailed insight into how Lewis acidity and Lewis basicity correlate to reactivity. The reactivity of frustrated Lewis pairs will be systematically discussed in context with selected reactions. The influence of major electronic modifications of the Lewis pairs is correlated with the ability to activate molecular hydrogen, to channel reaction kinetics and reaction pathways, or to achieve C(sp3)-H activations.First, we will describe how we entered this emerging field of research after quickly realizing that information was lacking on how the reactivity changes with modification of the frustrated Lewis pair. This led us to the development of a qualitative and quantitative structure-reactivity relationship in metal-free imine hydrogenations. The imine hydrogenation was utilized as the model reaction to experimentally determine the activation parameters of the FLP-mediated hydrogen activation for the first time. This kinetic study revealed autoinduced catalytic profiles when Lewis acids weaker than tris(pentafluorophenyl)borane were applied, opening up to study the Lewis base dependency within one system. With this knowledge of the interplay between Lewis acid strength and Lewis basicity, we developed methods for the hydrogenation of densely functionalized nitroolefins, acrylates, and malonates. Here, the reduced Lewis acidity needed to be counterbalanced by a suitable Lewis base to ensure efficient hydrogen activation. The opposite measure was necessary for the hydrogenation of unactivated olefins. For these, comparably less electron-releasing phosphanes were required to generate strong Brønsted acids by hydrogen activation. These systems displayed highly reversible hydrogen activation even at temperatures as low as -60 °C. A systematic study of these systems enabled the development of acceptorless dehydrocouplings of amines with silanes and dehydrogenations of aza-heterocycles by C(sp3)-H activations. Furthermore, the C(sp3)-H and π-activation was utilized to achieve cycloisomerizations by carbon-carbon and carbon-nitrogen bond formations. Lastly, new frustrated Lewis pair systems featuring weak Lewis bases as active components in the hydrogen activation were developed for the reductive deoxygenation of phosphane oxides and carboxylic acid amides.

Ruthenium(II)-Dithiocarbazates as Anticancer Agents: Synthesis, Solution Behavior, and Mitochondria-Targeted Apoptotic Cell Death.

The reaction of the Ru(PPh3 )3 Cl2 with HL1-3 -OH (-OH stands for the oxime hydroxyl group; HL1 -OH=diacetylmonoxime-S-benzyldithiocarbazonate; HL2 -OH=diacetylmonoxime-S-(4-methyl)benzyldithiocarbazonate; and HL3 -OH=diacetylmonoxime-S-(4-chloro)benzyl-dithiocarbazonate) gives three new ruthenium complexes [RuII (L1-3 -H)(PPh3 )2 Cl] (1-3) (-H stands for imine hydrogen) coordinated with dithiocarbazate imine as the final products. All ruthenium(II) complexes (1-3) have been characterized by elemental (CHNS) analyses, IR, UV-vis, NMR (1 H, 13 C, and 31 P) spectroscopy, HR-ESI-MS spectrometry and also, the structure of 1-2 was further confirmed by single crystal X-ray crystallography. The solution/aqueous stability, hydrophobicity, DNA interactions, and cell viability studies of 1-3 against HeLa, HT-29, and NIH-3T3 cell lines were performed. Cell viability results suggested 3 being the most cytotoxic of the series with IC50 6.9±0.2 μM against HeLa cells. Further, an apoptotic mechanism of cell death was confirmed by cell cycle analysis and Annexin V-FITC/PI double staining techniques. In this regard, the live cell confocal microscopy results revealed that compounds primarily target the mitochondria against HeLa, and HT-29 cell lines. Moreover, these ruthenium complexes elevate the ROS level by inducing mitochondria targeting apoptotic cell death.