Simple Alkenes Research Articles

High-Temperature Conversion of Olefins to Liquid Hydrocarbons on γ-Al2O3

Noncatalytic thermal conversion of light olefins proceeds at industrially relevant rates at temperatures above 450 °C and pressures above 50 bar. The discovery of solid acid oligomerization catalysts permitted the use of milder conditions (<300 °C) and significantly improved the octane rating. However, Brønsted acid catalysts deactivate and must be regenerated frequently. In this study, at reaction temperatures of about 250–450 °C and pressures of 1 to 40 bar, olefins react on γ-alumina to form higher molecular weight products. The rate of propylene is about ten times higher than that of ethylene. The products, however, are not a simple olefin oligomerization distribution, and many nonoligomer products are formed. The primary products undergo secondary reactions, including double bond isomerization and H-transfer, giving moderate selectivities for saturated products. Depending on the conversion, temperature, and pressure, the rate of ethylene conversion on alumina is more than 100 times that of thermal, noncatalytic conversion. The apparent activation energy for ethylene conversion is 55–75 kJ/mol, which is much lower than ∼244 kJ/mol observed for the thermal gas-phase reaction. On alumina, some reactants and products undergo disproportionation reactions. For example, propylene forms equal molar amounts of ethylene and iso-butene even at very low conversions. Lewis acid sites on γ-alumina have previously been proposed as the active site for double bond isomerization and H–D exchange. Thus, it seems likely that Lewis acid sites are also catalytic for olefin oligomerization and disproportionation reactions. With the γ-alumina catalyst, high liquid yields can be achieved with little formation of coke and minimal deactivation for at least several days.

Iron-Catalyzed Coupling of Alkenes and Enones: Sakurai-Michael-type Conjugate Addition of Catalytic Allyliron Nucleophiles.

The iron-catalyzed coupling of alkenes and enones through allylic C(sp3)-H functionalization is reported. This redox-neutral process employs a cyclopentadienyliron(II) dicarbonyl catalyst and simple alkene substrates to generate catalytic allyliron intermediates for 1,4-addition to chalcones and other conjugated enones. The use of 2,4,6-collidine as the base and a combination of triisopropylsilyl triflate and LiNTf2 as Lewis acids was found to facilitate this transformation under mild, functional group-tolerant conditions. Both electronically unactivated alkenes as well as allylbenzene derivatives could be employed as pronucleophilic coupling partners, as could a range of enones bearing electronically varied substituents.

Docking-migration: a powerful tool for radical-mediated difunctionalization of alkenes

<p indent="0mm">Alkene difunctionalization supplies a robust tool for the conversion of simple alkenes to complex molecules by simultaneously installing two different functional groups to alkenes. In particular, radical-mediated difunctionalization of alkenes has received extensive attention from synthetic chemists, because of the inherent features of mild reaction conditions and high product diversity. By taking advantage of designed bifunctional reagents, in which a radical donor and a migrating group are tethered by a linker, the docking-migration process proceeding through consecutive radical addition to alkene and intramolecular functional group migration provides an efficient strategy for alkene difunctionalization. The approach demonstrates broad scope of alkene substrates that activated and unactivated alkenes as well as complex alkenes are suitable substrates. This account summarizes the progress from our group in alkene difunctionalization relying on the docking-migration strategy.

Iodide-Assisted Pd Catalysis as an Attractive Alternative to Rh Catalysis for the Industrially Relevant Isoselective Hydroformylation of Simple Aliphatic Alkenes

AbstractThe hydroformylation of simple aliphatic alkenes, such as propylene, is one of the largest homogenous catalyzed processes in the chemical industry, producing over 10 million metric tons of different aldehydes each year. Typically, such processes are catalyzed by Co or Rh catalysts, yielding mostly linear aldehydes, such as n-butanal. However, the increasing demand for branched aldehydes, such as isobutanal, triggered further investigation to develop efficient isoselective protocols, which remain scarce. In this Synpacts article, we discuss our recent work on iodide-assisted Pd catalysis as an attractive alternative strategy for the development of isoselective methods. This article is presented considering the state of the art for Rh-catalyzed processes. Additionally, we discuss the limitations and challenges that need to be addressed in order to successfully transfer the technology to industry.1 Introduction2 State of the Art for the Isoselective Rh-Catalyzed Hydroformylation of Unbiased Aliphatic Alkenes2.1 Decomposition-Driven Isoselectivity2.2 Substrate-Dependent Isoselectivity2.3 Equiselective Catalysis2.4 Isoselective Rh Catalysts Bearing Small-Bite-Angle Ligands2.5 Isoselective Rh Catalyst Bearing a Tridentate Ligand2.6 Isoselective Catalysis Driven by Rh Encapsulation2.7 Isoselective Catalysis Driven by Specific Noncovalent Substrate–Ligand Interactions3 Pd-Catalyzed Isoselective Hydroformylation of Unbiased Aliphatic Alkenes3.1 Selectivity Patterns in Pd-Catalyzed Hydroformylation of Alkenes3.2 Unusual Iodide-Assisted Binuclear Pd(I)–Pd(I) Mechanism3.3 Development of Pd-Catalyzed Isoselective Hydroformylation of Unbiased Aliphatic Alkenes4 Conclusions and Outlook

Electrochemical detection of simple alkanes by utilizing a solid-state zirconia-based gas sensor

Solid-state gas sensors composed of complex oxide electrolytes offer great potential for analyzing various atmospheres at high temperatures. While relatively simple gas mixtures (H2O+N2, O2+N2) have been successfully studied by means of ZrO2-based sensors, the precise detection of more complex compounds represents a challenging task. In this work, we present our findings regarding the analysis of lower alkanes (CH4, C2H6, and C3H8) mixed with nitrogen as an inert gas, utilizing an amperometric ZrO2-based sensor. This sensor, serving as an electrochemical cell with a diffusion barrier, was tested at 500–600 °C to measure the limiting current, which depends on the gas composition and can be further used as a basis for calibration curves. In addition, the diffusion coefficients of the specified gas mixtures were successfully found and compared with references, confirming the applicability of the fabricated sensor for studying diffusion processes in wide concentration and temperature ranges.

Trimerization of Acetylene and Alkene: Rapid Access to Polyenes

Open AccessCCS ChemistryCOMMUNICATIONS22 Dec 2022Trimerization of Acetylene and Alkene: Rapid Access to Polyenes Boxiang Liu, Zhicong Lin, Yu Wang, Tairan Cheng, Tongxiang Cao and Shifa Zhu Boxiang Liu Google Scholar More articles by this author , Zhicong Lin Google Scholar More articles by this author , Yu Wang Google Scholar More articles by this author , Tairan Cheng Google Scholar More articles by this author , Tongxiang Cao Google Scholar More articles by this author and Shifa Zhu Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202202579 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Conjugated polyene motifs are ubiquitous in various natural products and functional molecules, however their synthesis is very challenging because of the required lengthy and time-consuming processes. We herein report an efficient approach for the synthesis of (E, E)-trienes via cationic rhodium catalysis using acetylene and simple alkenes bearing diverse directing groups as the starting materials. The reaction features high step economy, excellent functional group compatibility and exclusive stereoselectivity. Various directing groups such as carbonyl, sulfone, phosphate, and even hydroxyl and amino are compatible. Furthermore, the triene products allow versatile elaborations, providing rapid and convenient access to several important bioactive molecules, such as Vitamin A, (+)-Roxaticin and other complex polyenes. The mechanistic experiments show that the directing group on the alkene plays a crucial role in the reaction. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 0Issue jaPage: 1-22Supporting Information Copyright & Permissions© 2022 Chinese Chemical Society Downloaded 84 times PDF downloadLoading ...

Imidodiphosphorimidates (IDPis): Catalyst Motifs with Unprecedented Reactivity and Selectivity

AbstractThe conceptually designed imidodiphosphorimidates (IDPis) have emerged as one of the most potent classes of chiral acid catalysts. They are characterized by enzyme‐like, highly confined active site and high acidity, which underlie their wide‐reaching applications as Brønsted acid catalysts and as precatalysts for silylium Lewis acids. Many carbon‐carbon and carbon‐heteroatom bond formation reactions that were deemed intractable could now be attained with spectacular reactivity and selectivity. Substrates that are small, unbiased and/or possess insufficient reactivity such as simple alkenes could now be engaged. The high structural confinement is particularly invaluable to control stereo‐ and chemoselectivity. The well‐defined steric environment offers unique opportunity to control high‐energy but structurally unbiased cation intermediates such as the norbonyl cations. Beyond practical appeals such as good scalability as well as ease and modularity of preparation, the extremely low pre‐catalyst loadings required to achieve high turnover and stereoselectivity have also come to define a new frontier in organocatalysis.

Designed Iron Catalysts for Allylic C-H Functionalization of Propylene and Simple Olefins.

Propylene gas is produced worldwide by steam cracking on million-metric-ton scale per year. It serves as a valuable starting material for π-bond functionalization but is rarely applied in transition metal-catalyzed allylic C-H functionalization for fine chemical synthesis. Herein, we report that a newly-developed cationic cyclopentadienyliron dicarbonyl complex allows for the conversion of propylene to its allylic C-C bond coupling products under catalytic conditions. This approach was also found applicable to the allylic functionalization of simple α-olefins with distinctive branched selectivity. Experimental and computational mechanistic studies supported the allylic deprotonation of the metal-coordinated alkene as the turnover-limiting step and led to insights into the multifaceted roles of the newly designed ligand in promoting allylic C-H functionalization with enhanced reactivity and stereoselectivity.

Designed Iron Catalysts for Allylic C−H Functionalization of Propylene and Simple Olefins

AbstractPropylene gas is produced worldwide by steam cracking on million‐metric‐ton scale per year. It serves as a valuable starting material for π‐bond functionalization but is rarely applied in transition metal‐catalyzed allylic C−H functionalization for fine chemical synthesis. Herein, we report that a newly‐developed cationic cyclopentadienyliron dicarbonyl complex allows for the conversion of propylene to its allylic C−C bond coupling products under catalytic conditions. This approach was also found applicable to the allylic functionalization of simple α‐olefins with distinctive branched selectivity. Experimental and computational mechanistic studies supported the allylic deprotonation of the metal‐coordinated alkene as the turnover‐limiting step and led to insights into the multifaceted roles of the newly designed ligand in promoting allylic C−H functionalization with enhanced reactivity and stereoselectivity.

A monolithic azacalix[4]pyridine column for high-resolution and high-efficiency pressurized capillary electrochromatographic separation

Herein, a highly stable (NAllyl)4-bridged alyzacalix[4]pyridine monolithic column (nAC4P@capillary) was fabricated by copolymerizing nAC4P with GMA and EDMA into a stationary phase through a simple olefin addition reaction. The physicochemical properties of the prepared materials were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), energy dispersive X-ray (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). A wide range of analytes with various properties was well separated and demonstrated the synergistic effect of the various interaction sites. The maximum column efficiencies (Nmax) for all the analytes reached 62,368 plates/m, and the relative standard deviations (RSDs) of the daily retention times of alkylbenzenes, measured over six months were all lower than 5.63%. Non-covalent interaction analysis reveals that nAC4P@capillary can effectively combine the advantages of electronic configurations, π-π interactions, CH-π interactions, O–H…N hydrogen bonds and lone pair-π interactions, providing excellent prospects for high-performance chromatographic separation.

Iridium-Catalyzed Branch-Selective Hydroalkylation of Simple Alkenes with Malonic Amides and Malonic Esters

We report the iridium-catalyzed branch-selective hydroalkylation of simple alkenes such as aliphatic alkenes and aromatic alkenes with malonic amides and malonic esters under neutral reaction conditions. A variety of aliphatic alkenes and aromatic alkenes bearing bromine, chlorine, ester, 2-thienylcarboxylate, silyl, and phthalimide groups were all found to be suitable for this hydroalkylation. The combination of this method with Krapcho dealkoxycarbonylation realized a one-pot synthesis of β-substituted amide and ester from β-amide ester and malonic ester. The hydroalkylated products derived from malonic amides are suitable for further transformation. The finely tuned reaction conditions realized the selective transformation of hydroalkylated products to 1,3-diamines or monoamides with the same reagent. Deuterium labeling experiments and measurement of the kinetic isotope effect indicated that the catalytic cycle involves a reversible step and cleavage of the C-H bond is not a rate-determining step. Density functional theory calculations provided insight into the reaction mechanism, where the carboiridation step is followed by C-H reductive elimination.

Chiral Alcohols from Alkenes and Water: Directed Evolution of a Styrene Hydratase.

Enantioselective synthesis of chiral alcohols through asymmetric addition of water across an unactivated alkene is a highly sought-after transformation and a big challenge in catalysis. Herein we report the identification and directed evolution of a fatty acid hydratase from Marinitoga hydrogenitolerans for the highly enantioselective hydration of styrenes to yield chiral 1-arylethanols. While directed evolution for styrene hydration was performed in the presence of heptanoic acid to mimic fatty acid binding, the engineered enzyme displayed remarkable asymmetric styrene hydration activity in the absence of the small molecule activator. The evolved styrene hydratase provided access to chiral alcohols from simple alkenes and water with high enantioselectivity (>99 : 1 e.r.) and could be applied on a preparative scale.

Chiral Alcohols from Alkenes and Water: Directed Evolution of a Styrene Hydratase

AbstractEnantioselective synthesis of chiral alcohols through asymmetric addition of water across an unactivated alkene is a highly sought‐after transformation and a big challenge in catalysis. Herein we report the identification and directed evolution of a fatty acid hydratase from Marinitoga hydrogenitolerans for the highly enantioselective hydration of styrenes to yield chiral 1‐arylethanols. While directed evolution for styrene hydration was performed in the presence of heptanoic acid to mimic fatty acid binding, the engineered enzyme displayed remarkable asymmetric styrene hydration activity in the absence of the small molecule activator. The evolved styrene hydratase provided access to chiral alcohols from simple alkenes and water with high enantioselectivity (&gt;99 : 1 e.r.) and could be applied on a preparative scale.

Zwitterionic Diphenylphosphinyl Amidate as a Powerful Photoinduced Hydrogen-Atom-Transfer Catalyst for C-H Alkylation of Simple Alkanes.

The chemical and physical properties of amides change substantially when the electron-withdrawing groups attached to the nitrogen are varied. Herein, we report the superior performance of N-diphenylphosphinyl 1,2,3-triazolium amidate as a photoinduced hydrogen-atom transfer catalyst compared to its N-benzoyl analog. A binary catalyst system of the phosphinyl amidate and an Ir-based photocatalyst enables the alkylation of unbiased C-H bonds.

Ruthenium-catalyzed intermolecular alkene-alkyne couplings in biologically relevant media.

Cationic cyclopentadienyl Ru(ii) catalysts can efficiently promote mild intermolecular alkyne-alkene couplings in aqueous media, even in the presence of different biomolecular components, and in complex media like DMEM. The method can also be used for the derivatization of amino acids and peptides, therefore proposing a new way to label biomolecules with external tags. This C-C bond-forming reaction, based on simple alkene and alkyne reactants, can now be added to the toolbox of bioorthogonal reactions promoted by transition metal catalysts.

Ammonolytic transfer dehydrogenation of amines and amides: a versatile method to valorize nitrogen compounds to nitriles.

The dehydrogenation of amines has been identified as an efficient method for nitrile synthesis. At present, this approach is restricted to (oxidative) dehydrogenations of primary amines, most often with specialized homogeneous catalysts. In this work, amines were transfer dehydrogenated to nitriles using simple and cheap alkenes (e.g. ethylene or propene) as hydrogen scavengers. The scope was expanded to secondary amines, tertiary amines and even aldehydes. Additional nitrogen is built in from NH3. The versatility of the process was proven by coupling it to the ammonolysis of secondary amides. This enabled us to recycle long-chain polyamides (LCPA) into monomeric compounds, i.e. α,ω-amidonitriles and dinitriles. Reactions were performed with a recyclable heterogeneous Pt catalyst, at 200 °C and with limited addition of NH3 and ethylene. High yields of up to 94% were obtained for the corresponding nitriles.

Nanoscale chemical patterning of graphite at different length scales.

Chemical patterning surfaces is relevant in several different domains of science and technology with exciting possibilities in electronics, catalysis, sensing, and photonics. Here, we present a novel strategy for chemical patterning of graphite using a combination of covalent and non-covalent approaches. Building on our previous work, where self-assembled monolayers of linear alkanes were used as sacrificial masks for directing the covalent anchoring of aryl groups to the graphite surface in sub-10 nm arrays, we present a modified design of a template alkane with alkoxy terminal groups which allowed better pattern transfer fidelity in comparison to simple linear alkanes. We also explored the use of chronoamperometry (CA) instead of previously used cyclic voltammetry (CV) for the functionalization process, which enabled patterning of the graphite surface at two-different length scales: few hundred nanometer circular patterns interspersed with sub-10 nm linear arrays. The covalent chemical patterning process has been studied in detail using CV and CA measurements whereas the patterned substrates have been thoroughly characterized using Raman spectroscopy, scanning tunnelling microscopy (STM) and atomic force microscopy (AFM). Based on the comparison between the pattern transfer fidelity of previously studied alkanes and newly synthesized alkoxy alkane, we discuss plausible molecular mechanism of pattern transfer.

Practical synthesis of allylic amines via nickel-catalysed multicomponent coupling of alkenes, aldehydes, and amides.

Molecules with an allylic amine motif provide access to important building blocks and versatile applications of biologically relevant chemical space. The need for diverse allylic amines requires the development of increasingly general and modular multicomponent reactions for allylic amine synthesis. Herein, we report an efficient catalytic multicomponent coupling reaction of simple alkenes, aldehydes, and amides by combining nickel catalysis and Lewis acid catalysis, thus providing a practical, environmentally friendly, and modular protocol to build architecturally complex and functionally diverse allylic amines in a single step. The method is remarkably simple, shows broad functional-group tolerance, and facilitates the synthesis of drug-like allylic amines that are not readily accessible by other methods. The utilization of accessible starting materials and inexpensive Ni(ii) salt as the alternative precatalyst offers a significant practical advantage. In addition, the practicality of the process was also demonstrated in an efficient, gram-scale preparation of the prostaglandin agonist.

C-C bond formation via photocatalytic direct functionalization of simple alkanes.

The direct functionalization of alkanes represents a very important challenge in the goal to develop more atom-efficient and clean C-C bond forming reactions. These processes, however, are hampered by the low reactivity of the aliphatic C-H bonds. Photocatalytic processes based on hydrogen atom transfer C-H bond activation strategies have become a useful tool to activate and functionalize these inert compounds. In this article, we summarize the main achievements in this field applied to the development of C-C bond forming reactions, and we discuss the key mechanistic features that enable these transformations.

Prevotella: A Key Player in Ruminal Metabolism.

Ruminants are foregut fermenters that have the remarkable ability of converting plant polymers that are indigestible to humans into assimilable comestibles like meat and milk, which are cornerstones of human nutrition. Ruminants establish a symbiotic relationship with their microbiome, and the latter is the workhorse of carbohydrate fermentation. On the other hand, during carbohydrate fermentation, synthesis of propionate sequesters H, thus reducing its availability for the ultimate production of methane (CH4) by methanogenic archaea. Biochemically, methane is the simplest alkane and represents a downturn in energetic efficiency in ruminants; environmentally, it constitutes a potent greenhouse gas that negatively affects climate change. Prevotella is a very versatile microbe capable of processing a wide range of proteins and polysaccharides, and one of its fermentation products is propionate, a trait that appears conspicuous in P. ruminicola strain 23. Since propionate, but not acetate or butyrate, constitutes an H sink, propionate-producing microbes have the potential to reduce methane production. Accordingly, numerous studies suggest that members of the genus Prevotella have the ability to divert the hydrogen flow in glycolysis away from methanogenesis and in favor of propionic acid production. Intended for a broad audience in microbiology, our review summarizes the biochemistry of carbohydrate fermentation and subsequently discusses the evidence supporting the essential role of Prevotella in lignocellulose processing and its association with reduced methane emissions. We hope this article will serve as an introduction to novice Prevotella researchers and as an update to others more conversant with the topic.