Transformation Of Alkenes Research Articles

Nickel-Catalyzed Reductive Alkenylation of Enol Derivatives: A Versatile Tool for Alkene Construction.

ConspectusKetone-to-alkene transformations are essential in organic synthesis, and transition-metal-catalyzed cross-coupling reactions involving enol derivatives have become powerful tools to achieve this goal. While substantial progress has been made in nucleophile-electrophile reactions, recent developments in nickel-catalyzed reductive alkenylation reactions have garnered increasing attention. These methods accommodate a broad range of functional groups such as aldehyde, ketone, amide, alcohol, alkyne, heterocycles, and organotin compounds, providing an efficient strategy to access structurally diverse alkenes. This Account primarily highlights the contributions from our laboratory to this growing field while also acknowledging key contributions from other researchers.Our early efforts in this area focused on coupling radical-active substrates, such as α-chloroboronates. This method follows the conventional radical chain mechanism, resulting in facile access to valuable allylboronates. Encouraged by these promising results, we subsequently expanded the substrate scope to encompass radical-inactive compounds. By developing new strategies for controlling cross-selectivity, we enabled the coupling of Csp3 electrophiles (e.g., alcohols and sulfonates), Csp2 electrophiles (e.g., bromoalkenylboronates and acyl fluorides), and heavier group-14 electrophiles like chlorosilanes and chlorogermanes with alkenyl triflates. These advances have provided efficient synthetic routes to a wide range of valuable products, including aliphatic alkenes, enones, dienylboronates, and silicon- and germanium-containing alkenes. Notably, these methods are particularly effective for synthesizing functionalized cycloalkenes, which are traditionally challenging to obtain through conventional methods involving alkenyl halide or organometallic couplings. We have also extended the scope of enol derivatives from triflates to acetates. These compounds are among the most accessible, stable, cost-effective, and environmentally friendly reagents, while their application in cross-coupling has been hampered by low reactivity and selectivity challenges. We showcased that by the use of a Ni(I) catalyst, alkenyl acetates could undergo reductive alkylation with a broad range of alkyl bromides, yielding diverse cyclic and acyclic aliphatic alkenes.Furthermore, our work has demonstrated that reductive coupling of enol derivatives with alkenes provides a highly appealing alternative for alkene synthesis. Particularly, this approach offers opportunity to address the regioselectivity challenges encountered in conventional alkene transformations. For instance, achieving regioselective hydrocarbonation of aliphatic 1,3-dienes has been a longstanding challenge in synthetic chemistry. By using a phosphine-nitrile ligand, we developed a nickel-catalyzed reductive alkenylation of 1,3-dienes with alkenyl triflates, delivering a diverse array of 1,4-dienes with high 1,2-branch selectivity (>20:1) while preserving the geometry of the C3-C4 double bond. Additionally, our investigations laid the foundation for enantioselective reductive alkenylation methodologies, offering new pathways for constructing enantioenriched diketones as well as complex carbo- and heterocyclic compounds. The introduced alkenyl functionality can be further diversified, enhancing molecular diversity and complexity.

Surface-decorated magnetite nanoparticles with dioxidomolybdenum(VI) complexes as a catalyst for alkene epoxidation

Two dioxidomolybdenum(VI) complexes, denoted as [(MoO2)2(L1)] 1 and [(MoO2)2(L2)] 2, were successfully synthesized and characterized. Subsequently, these complexes were immobilized onto the surface of Fe3O4@SiO2-NH2, yielding supported compounds [(MoO2)2(L1)]@Fe3O4@SiO2-NH23 and [(MoO2)2(L2)]@Fe3O4@SiO2-NH24. A range of analytical techniques was employed to thoroughly characterize all synthesized compounds. The effectiveness of the developed supported catalysts in catalyzing the epoxidation of alkenes with hydrogen peroxide (H2O2) as the oxidant was assessed. Moreover, the magnetic properties of the supported compounds were assessed before and after catalytic reactions. It was observed that the magnetic properties exhibited slight alteration following the catalytic cycles. Remarkably, the supported catalysts demonstrated remarkable performance, affording excellent conversion rates along with favorable selectivity towards epoxide products. In addition, the catalysts were found to be reusable for up to seven successive cycles in the transformation of olefins and could be effectively recovered from the reaction mixture using an external magnet.

Quantification of competitive adsorptions between sulfur and olefinic model compounds representative of a FCC gasoline over a CoMoS/Al2O3 catalyst: Theoretical and experimental approaches

The reinforcement of regulations for the production of cleaner fuels along with the larger demand for energy urge us to optimize the HDS processes. The transformation of various olefins alone and in mixture with sulfur compounds was investigated over a CoMoS/Al2O3 catalyst under HDS of FCC gasoline operating conditions. A reactivity scale was established with hex-1-ene being more reactive than 4methylpent-1-en was more reactive than 4-methylpent-1-ene, 3,3-dimethylbut-1-ene and 2,3-dimethylbut-2-ene. The transformation of these olefins involves two main reactions ie isomerization and hydrogenation. In the presence of sulfur compounds (3-methythiophene and benzothiophene), a mutual inhibiting effect was observed with benzothiophene 3,3- dimethylbut-1-ene being respectively the most inhibiting sulfur and olefin compounds. These results were explained with a unique kinetic model from which the adsorption constants calculated were the highest for benzothiophene and 3,3-dimethylbut-1-ene.

(Invited) The Activation of Alkanes at Electrochemical Interfaces Using Real-Time Control of Potentials: Novel Avenues for Energy Storage and Sustainable Chemical Manufacturing

Producing fuels and chemicals using renewable electricity holds the promise to enable a truly sustainable circular economy based on sustainably produced carriers of electrical energy and sustainably produced chemicals. The science which allows us to link electricity to chemical transformations, electrocatalysis, remains chiefly focused on the electricity-driven transformation of small inorganic molecules such as CO2, H2O, N2, as well as the oxidation and reduction of alcohols. However, comprehensive electrification of society will require electrocatalytic reactions that can promote the central processes that sustain today’s society: alkane transformations. In this presentation, I will show how fundamental understanding of the interfacial processes occurring in electrocatalytic reactions, combined with monolayer-sensitive differential electrochemical mass spectrometry, allows us to independently control the elementary steps (adsorption, transformation, desorption) of complex alkane transformation reactions, allowing for the room-temperature fragmentation of ethane into methane, as well as for enabling the extraction of the chemical energy stored in alkanes in the form of electricity. I will show how we can apply these technologies to expand the reaction scope of electrocatalysis, allowing for novel avenues in energy storage, chemical synthesis and plastics recycling.

Photocatalytic Three-Component Acylcarboxylation of Alkenes with CO2.

γ-Keto acid is a valuable chemical motif in a wide range of fields including organic, biological, and medicinal chemistry. However, its single-step synthesis is challenging because of the mismatch of the carbonyl polarity and low tolerance of carboxylic acids. Herein, we report the single-step syntheses of γ-keto acids using alkenes and CO2. Our photocatalytic system enabled the transformation of alkenes under mild conditions in high yields (up to 95%) with broad substrate generality (35 examples).

Efficient methane oxidation to formaldehyde via photon–phonon cascade catalysis

The oxidation of methane to value-added chemicals provides an opportunity to use this abundant feedstock for sustainable petrochemistry. Unfortunately, such technologies remain insufficiently competitive due to a poor selectivity and a low yield rate for target products. Here we show a photon–phonon-driven cascade reaction that allows for methane conversion to formaldehyde with an unprecedented productivity of 401.5 μmol h−1 (or 40,150 μmol g−1 h−1) and a high selectivity of 90.4% at 150 °C. Specifically, with a ZnO catalyst decorated with single Ru atoms, methane first reacts with water to selectively produce methyl hydroperoxide via photocatalysis, followed by a thermodecomposition step yielding formaldehyde. Single Ru atoms, serving as electron acceptors, improve charge separation and promote oxygen reduction in photocatalysis. This reaction route with minimized energy consumption and high efficiency suggests a promising pathway for the sustainable transformation of light alkanes.

Cyclization via Metal-Catalyzed Hydrogen Atom Transfer/Radical-Polar Crossover

AbstractCatalytic transformations of alkenes via the metal-hydride hydrogen atom transfer (MHAT) mechanism have notably advanced synthetic organic chemistry. This Account focuses on MHAT/radical-polar crossover (MHAT/RPC) conditions, offering a novel perspective on generating electrophilic intermediates and facilitating various intramolecular reactions. On using cobalt hydrides, the MHAT mechanism displays exceptional chemoselectivity and functional group tolerance, making it invaluable for the construction of complex biologically relevant molecules under mild conditions. Recent developments have enhanced regioselectivity and expanded the scope of MHAT-type reactions, enabling the formation of cyclic molecules via hydroalkoxylation, hydroacyloxylation, and hydroamination. Notably, the addition of an oxidant to traditional MHAT systems enables the synthesis of rare cationic alkylcobalt(IV) complexes, bridging radical mechanisms to ionic reaction systems. This Account culminates with examples of natural product syntheses and an exploration of asymmetric intramolecular hydroalkoxylations, highlighting the ongoing challenges and opportunities for future research to achieve higher enantioselectivity. This comprehensive study revisits the historical evolution of the MHAT mechanism and provides a groundwork for further innovations on the synthesis of structurally diverse and complex natural products.1 Introduction2 Intramolecular Hydroalkoxylation and Hydroacyloxylation Reactions3 Intramolecular Hydroamination Reactions4 Intramolecular Hydroarylation Reactions5 Deprotective Cyclization6 Asymmetric Intramolecular Hydroalkoxylation7 Conclusion

Quantum Chemical Modeling of Reactions of the Catalytic Transformation of Alkanes

Quantum Chemical Modeling of Reactions of the Catalytic Transformation of Alkanes

Transformation of Light Alkanes into High-Value Aromatics

This research work is focused on the transformation of light alkane (propane) into high-value aromatics using gallo-alumino-silicate catalysts. Two sets of gallo-alumino-silicates were synthesized for this study. In the first set, the ratio of Ga/(Al+Ga) was modified, while the Si/(Al+Ga) ratio was held constant. In the subsequent set, the Si/(Al+Ga) ratio was adjusted, while maintaining a consistent Ga/(Al+Ga) ratio. This approach aimed to directly assess the impact of each ratio on catalyst performance. The comprehensive characterization of all catalysts was conducted using various instrumental techniques, i.e., BET surface area, XRD, NH3-TPD, 27Al, 71Ga and 29Si MAS NMR, and XPS. A gradual reduction in the percentage of crystallinity and rise in meso-surface area was noticed with a rise in Ga/(Al+Ga) ratio. The total acidity (NH3-TPD) demonstrated a decline as the Si/(Al+Ga) ratio increased, attributed to an overall decline in Al3+ or Ga3+ species. The XPS intensity of the Ga 2p3/2 peak rose in correlation with an elevated ratio of Ga/(Al+Ga), suggesting the formation of extra-framework Ga species. The propane conversion, aromatic yield, and aromatization/cracking ratio exhibited an increase with an increasing Ga/(Al+Ga) ratio, reaching an optimum value of 0.46 before declining. Conversely, an appreciable drop in the conversion of propane and yield of aromatics was detected with the rise in Si/(Al+Ga) ratio, attributing to the decline in acidity. The catalyst having a Ga/(Al+Ga) ration of 0.46 exhibited the highest propane conversion and aromatic yield of 83.0% and 55.0% respectively.

Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities

AbstractOxidative alkene functionalization reactions are a fundamental class of complexity‐building organic transformations. However, the majority of established approaches rely on electrophilic reagents that limit the diversity of groups that can be installed. Recent advances have established a new approach that instead relies on the transformation of alkenes into thianthrene‐derived cationic electrophiles. These linchpin intermediates can be generated selectively and undergo a diverse array of mechanistically distinct reactions with abundant nucleophiles. Taken together, this unlocks a suite of net oxidative alkene transformations that have been elusive using conventional strategies. This Minireview describes these advances and is organized around the three distinct synthons formally accessible from alkenes via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout the Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene‐derived electrophiles and highlight the mechanistic origins of these distinctions wherever possible.

Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities.

Oxidative alkene functionalization reactions are a fundamental class of complexity-building organic transformations. However, the majority of established approaches rely on electrophilic reagents that limit the diversity of groups that can be installed. Recent advances have established a new approach that instead relies on the transformation of alkenes into thianthrene-derived cationic electrophiles. These linchpin intermediates can be generated selectively and undergo a diverse array of mechanistically distinct reactions with abundant nucleophiles. Taken together, this unlocks a suite of net oxidative alkene transformations that have been elusive using conventional strategies. This Minireview describes these advances and is organized around the three distinct synthons formally accessible from alkenes via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout the Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene-derived electrophiles and highlight the mechanistic origins of these distinctions wherever possible.

Terminal C(sp3)-H borylation through intermolecular radical sampling.

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp3)-H bonds and thereby convert feedstock alkanes into value-added fine chemicals. Nevertheless, the high reactivity of HAT reagents, coupled with the small differences among various C(sp3)-H bond strengths, renders site-selective transformations of straight-chain alkanes a great challenge. Here, we present a photocatalytic intermolecular radical sampling process for the iron-catalyzed borylation of terminal C(sp3)-H bonds in substrates with small steric hindrance, including unbranched alkanes. Mechanistic investigations have revealed that the reaction proceeds through a reversible HAT process, followed by a selective borylation of carbon radicals. A boron-sulfoxide complex may contribute to the high terminal regioselectivity observed.

Catalytic transformations of alkenes via nickelacycles

This review summarizes recent developments in nickel-catalyzed transformations of alkenes via nickelacycles, highlighting the advantages and challenges of this innovative strategy.

Experimental and Theoretical Investigation of Alkene Transformations in Oceanic Hydrothermal Fluids: A Mechanistic Study of Styrene

AbstractNatural organic matter plays an important role in oceanic hydrothermal systems through a combination of geological and chemical processes. However, identifying the hydrothermal pathways of organic compounds is still quite limited, preventing us from understanding how organic matter is transformed in hydrothermal systems. In this study, we focus on the reaction pathways of alkenes, which represent a key functional group intermediate linking the most abundant hydrocarbons in seafloor hydrothermal environments. Three major pathways are observed for alkenes under mild hydrothermal conditions, including hydration, oxidation, and dimerization. The pathway distributions of alkenes can be affected by the presence of dissolved metal salts; hydration of alkenes is driven by metal ions via the change of solution pH, while alkene dimerization is controlled by pH and the type of metal cations and complexes. Overall, this study identifies alkene hydrothermal pathways and highlights the important roles of metal salts in controlling hydrothermal transformations.

Back Cover

This cover picture shows a new electrophotocatalytic intermolecular reductive 1,2‐diarylation of alkenes with aryl halides and cyanoaromatics. Upon use of a synergistic cathodic reduction and visible‐light photoredox catalysis, a magpie bridge (two new Csp3–Csp2 bonds) was built for the Niulang and the Zhinyu to meet on the Chinese Valentine's Day (Big hugs among multiple reaction components to enable alkene intermolecular reductive 1,2‐diarylation). This method features broad substrate scope, excellent functional group compatibility, and excellent selectivity, and provides a conceptually novel electrophotocatalytic alkene difuncrionalization strategy that consists of undivided cell and divided cell methodologies for highly valuable transformations of alkenes. More details are discussed in the article by Li et al. on page 1921—1930.image

Electrocatalytic Scission of Unactivated C(sp3)-C(sp3) Bonds through Real-Time Manipulation of Surface-Bound Intermediates.

Electrocatalysis plays a critical role in future technologies for energy storage and sustainable synthesis, but the scope of reactions achievable using electricity remains limited. Here, we demonstrate an electrocatalytic approach to cleave the C(sp3)-C(sp3) bond in ethane at room temperature over a nanoporous Pt catalyst. This reaction is enabled by time-dependent electrode potential sequences, combined with monolayer-sensitive in situ analysis, which allows us to gain independent control over ethane adsorption, oxidative C-C bond fragmentation, and reductive methane desorption. Importantly, our approach allows us to vary the electrode potential to promote the fragmentation of ethane after it is bound to the catalyst surface, resulting in unprecedented control over the selectivity of this alkane transformation reaction. Steering the transformation of intermediates after adsorption constitutes an underexplored lever of control in catalysis. As such, our findings widen the parameter space for catalytic reaction engineering and open the door to future sustainable synthesis and electrocatalytic energy storage technologies.

Novel Co5 Cluster Based Triazole Bridged Cobalt‐Fluorophosphate: Synthesis, Structure, Magnetic and Heterogeneous Catalytic Epoxidation Studies

AbstractA novel triazole bridged cobalt fluorophosphate coordination polymer with the formula {Co5(1,2,4‐triazole)2(OH)2(PO3F)4}n has been synthesized. Single crystal X‐ray studies reveal that the compound comprises of Co5 clusters which ultimately build the whole framework, here all cobalt centers are in octahedral geometry established from continuous shape analysis. All the cobalt centers are in Co(II) oxidation state and the results are supported by the bond valence sum (BVS) calculation. The sample has been characterized by single crystal X‐ray, powder X‐ray, FTIR and TGA analysis. The compound was tested for olefin catalysis performance and magnetism. Magnetization measurements reveal overall antiferromagnetic interactions among the Co(II) ions. The compound is very active in the catalytic transformation of olefins to their corresponding epoxides. Catalytic epoxidation studies reveal that cyclohexene and styrene can be converted up to 97 % with almost 65 % selectivity of products with higher TON numbers.

Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers

Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the synthesis of practically useful products of alkene transformations, such as dimers, oligomers, and polymers. Here we studied the catalytic activity of structurally diverse zirconocenes (L2ZrCl2, L = Cp, C5Me5, Ind, L2 = Me2CCp2, Me2SiCp2, Me2C2Cp2, rac-Me2CInd2, rac-H4C2Ind2, BIPh(Ind)2, H4C2[THInd]2), and co-catalysts activating the system, namely HAlBui2, MMAO-12, and (Ph3C)[B(C6F5)4], at low activator/Zr ratios in a 1-hexene oligomerization reaction. The influence of catalyst structure and system composition on the alkene conversion, the type of products, and the reaction stereoselectivity were investigated. The composition of hydride intermediates formed in the L2ZrCl2-HAlBui2-activator system (L2 = ansa-Me2CCp2, Ind) was studied by NMR spectroscopy. Participation of the bis-zirconium hydride complex as the precursor of catalytically active sites of the alkene dimerization reaction was shown.

Chalcogen Bonding Catalysis with Phosphonium Chalcogenide (PCH).

ConspectusThe exploration of new catalysis concepts and strategies to drive chemical reactions is of vital importance for the sustainable development of organic synthesis. Recently, chalcogen bonding catalysis has emerged as a new concept for organic synthesis and has been demonstrated to be an important synthetic tool capable of addressing elusive reactivity and selectivity issues. This Account describes our progress in the research field of chalcogen bonding catalysis, including (1) the discovery of phosphonium chalcogenide (PCH) as highly efficient chalcogen bonding catalyst; (2) the development of "chalcogen-chalcogen bonding catalysis" and "chalcogen···π bonding catalysis" modes; (3) the demonstration that chalcogen bonding catalysis with PCH can activate hydrocarbons to achieve cyclization and coupling reactions of alkenes; (4) the discovery of unusual results that chalcogen bonding catalysis with PCH can solve elusive reactivity and selectivity issues that are inaccessible by classic catalysis approaches; and (5) the elucidation of chalcogen bonding mechanisms.With PCH catalysts, we systematically studied their chalcogen bonding properties, the relationship between structure and catalysis, and their application in facilitating a diverse array of reactions. Enabled by chalcogen-chalcogen bonding catalysis, an efficient assembly reaction of three molecules of β-ketoaldehyde and one indole derivative in a single operation was realized, delivering heterocycles with a newly constructed seven-membered ring. In addition, a Se···O bonding catalysis approach achieved an efficient synthesis of calix[4]pyrroles. We developed a "dual chalcogen bonding catalysis" strategy to solve reactivity and selectivity issues in the Rauhut-Currier-type reactions and related cascade cyclizations, thus shifting conventionally covalent Lewis base catalysis to a cooperative Se···O bonding catalysis approach. This strategy enables the cyanosilylation of ketones to take place in the presence of a ppm-level amount of PCH catalyst loading. Furthermore, we established chalcogen···π bonding catalysis for catalytic transformation of alkenes. In the research field of supramolecular catalysis, the activation of hydrocarbons such as alkenes by weak interactions is a highly interesting unresolved topic. We showed that the Se···π bonding catalysis approach could efficiently activate alkenes to achieve both coupling and cyclization reactions. Chalcogen···π bonding catalysis with PCH catalysts is particularly highlighted by the capability of facilitating strong Lewis-acid inaccessible transformations, such as the controlled cross coupling of triple alkenes. Overall, this Account presents a panoramic view of our research on chalcogen bonding catalysis with PCH catalysts. The works described in this Account provide a significant platform to solve synthetic problems.

Coordination Assistance: A Powerful Strategy for Metal-Catalyzed Regio- and Enantioselective Hydroalkynylation of Internal Alkenes

ConspectusAlkenes are versatile compounds that are readily available on a large scale from industry or through organic synthesis. The widespread occurrence of alkenes provides the continuous impetus for the development of catalytic asymmetric alkene hydrofunctionalizations, which enables expeditious construction of complex chiral molecules from readily available starting materials. Catalytic asymmetric hydrofunctionalization of internal alkenes presents a notable challenge, due to their low reactivity, many potential side reactions, and the simultaneous control of the regio-, diastereo-, and enantioselectivities.Dehydroamino acids and enamides are among the first substrates that provide notable enantioselectivities in catalytic asymmetric hydrogenation. The crucial importance of an amide coordinating group is established by a series of classical mechanistic studies. This initial success greatly stimulated further development for catalytic hydrogenation and hydrofunctionalization. Building on these pioneering works in asymmetric hydrogenation as well as related hydrofunctionalizations, we have adopted coordination assistance as a powerful tool to address the challenges associated with the asymmetric hydrofunctionalization of internal alkenes. Using a functional group on the alkene substrate as a native coordinating group, a two-point binding mode of the substrate to the metal center effectively enhances the reactivity and facilitates the control of regio-, diastereo- and enantioselectivities. Through this strategy, we have developed a number of alkene hydrofunctionalization methods with excellent regio-, diastereo-, and enantiocontrols.In this Account, we summarize the recent advance in our lab using coordination assistance as a key element to achieve regio- and enantioselective hydroalkynylation of internal alkenes. First, we describe our early work aimed at controlling the regio- and enantioselectivity of hydroalkynylation using disubstituted enamide as the substrate. Both α- and β-alkynylation were achieved by channeling the reaction pathway into a Chalk-Harrod or modified Chalk-Harrod mechanism. Next, we discuss the further development of catalysts to achieve regiodivergent and enantioselective hydroalkynylation of trisubstituted enamide to access vicinal stereocenters and quaternary carbon stereocenters. We also discuss the hydroalkynylation of α,β-unsaturated amides to achieve unconventional site-selectivity through a combination of alkene isomerization and regioselective hydroalkynylation. This provides the basis for the construction of a remote quaternary carbon stereocenter through catalytic hydroalkynylation of trisubstituted β,γ-unsaturated amides. We further show that this controlling principle is applicable to terminal alkene with a coordinating group as well. A ligand-controlled mechanism shift is discussed for the enantioselective alkynylation at the terminal and internal position of 1,1,-disubstituted alkenes. Finally, we briefly mention the application of coordination assistance to other hydrofunctionalizations such as hydroboration and hydrosilylation, where previously inaccessible reactivity and selectivity were achieved. Collectively, these catalytic methods demonstrate the power of coordination assistance for enantioselective hydrofunctionalizations. We anticipate that this strategy will create a platform to enable diverse enantioselective alkene transformations.