Carboxylation of alkenes and alkynes using CO2 as a reagent: an overview

2021 ◽  
Vol 25 ◽  
Author(s):  
Rupak Chatterjee ◽  
Asim Bhaumik
Keyword(s):  
Co2 Fixation ◽  
Bond Activation ◽  
Reaction Products ◽  
Co2 Utilization ◽  
Reaction Conditions ◽  
Catalytic Systems ◽  
Chemical Inertness ◽  
Commodity Chemicals ◽  
High Thermodynamic Stability ◽  
Recent Developments

: CO2 fixation reactions are of paramount interest both from economical and environmental perspectives. As an abundant, non-toxic, and renewable C1 feedstock, CO2 can be utilized for the synthesis of fuels and commodity chemicals under elevated reaction conditions. The major challenge in the CO2 utilization reactions is its chemical inertness due to high thermodynamic stability and kinetic barrier. The carboxylation of unsaturated hydrocarbons with CO2 is an important transformation as it forms high-value reaction products having industrial as well as medicinal importance. This mini-review is mainly focused on the recent developments in the homogeneously and heterogeneously catalyzed carboxylation of alkenes and alkynes by using carbon dioxide as a reagent. We have highlighted various types of carboxylation reactions of alkenes and alkynes involving different catalytic systems, which comprise mainly C-H bond activation, hydrocarboxylation, carbocarboxylation, heterocarboxylation, and ring-closing carboxylation, including visible-light assisted synthesis processes. The mechanistic pathways of these carboxylation reactions have been described. Moreover, challenges and future perspectives of these carboxylation reactions are discussed.

scholarly journals Photo-Induced Thiolate Catalytic Activation of Inert Caryl-Hetero Bonds for Radical Borylation

2020 ◽  
Author(s):  
Shun Wang ◽  
Hua Wang ◽  
Burkhard Koenig
Keyword(s):  
Bond Activation ◽  
Reducing Power ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Catalytic Activation ◽  
Cross Coupling Reactions ◽  
Recent Developments ◽  
Leaving Groups ◽  
Metal Catalyzed

Cross-coupling reactions are essential tools in modern synthesis of drugs, natural products and materials. The recent developments in photocatalytic radical generation have improved and expanded the classic metal-catalyzed cross coupling reactions even further. However, for sp<sup>2</sup> cross coupling reactions aryl halides or related active leaving groups, such as triflates, are required. Substituted arenes bearing strong C-X bonds remain inert to current methods. We describe now a new thiolate photocatalysis for the activation of inert substituted arenes in ipso-borylation reactions. This catalytic system exhibits strong reducing power and allows the borylation of stable C<sub>aryl</sub>−F, C<sub>aryl</sub>−O, C<sub>aryl</sub>-N and C<sub>aryl</sub>−S bonds, which are considered as chemically stable at mild reaction conditions. Our method considerably widens the available substrate scope of aryl radical precursors and we anticipate that this report will inspire new chemistry based on inert chemical bond activation.

scholarly journals Photo-Induced Thiolate Catalytic Activation of Inert Caryl-Hetero Bonds for Radical Borylation

2020 ◽  
Author(s):  
Shun Wang ◽  
Hua Wang ◽  
Burkhard Koenig
Keyword(s):  
Bond Activation ◽  
Reducing Power ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Catalytic Activation ◽  
Cross Coupling Reactions ◽  
Recent Developments ◽  
Leaving Groups ◽  
Metal Catalyzed

Cross-coupling reactions are essential tools in modern synthesis of drugs, natural products and materials. The recent developments in photocatalytic radical generation have improved and expanded the classic metal-catalyzed cross coupling reactions even further. However, for sp<sup>2</sup> cross coupling reactions aryl halides or related active leaving groups, such as triflates, are required. Substituted arenes bearing strong C-X bonds remain inert to current methods. We describe now a new thiolate photocatalysis for the activation of inert substituted arenes in ipso-borylation reactions. This catalytic system exhibits strong reducing power and allows the borylation of stable C<sub>aryl</sub>−F, C<sub>aryl</sub>−O, C<sub>aryl</sub>-N and C<sub>aryl</sub>−S bonds, which are considered as chemically stable at mild reaction conditions. Our method considerably widens the available substrate scope of aryl radical precursors and we anticipate that this report will inspire new chemistry based on inert chemical bond activation.

scholarly journals Selective Styrene Oxidation to Benzaldehyde over Recently Developed Heterogeneous Catalysts

Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1680
Author(s):  
Marta A. Andrade ◽  
Luísa M. D. R. S. Martins
Keyword(s):  
Heterogeneous Catalysts ◽  
Carbon Materials ◽  
Oxygen Species ◽  
Styrene Oxidation ◽  
Reaction Conditions ◽  
Reactive Metal ◽  
Catalytic Systems ◽  
Tert Butyl Hydroperoxide ◽  
Metal Organic ◽  
Important Intermediate

The selective oxidation of styrene under heterogeneous catalyzed conditions delivers environmentally friendly paths for the production of benzaldehyde, an important intermediate for the synthesis of several products. The present review explores heterogeneous catalysts for styrene oxidation using a variety of metal catalysts over the last decade. The use of several classes of supports is discussed, including metal–organic frameworks, zeolites, carbon materials and silicas, among others. The studied catalytic systems propose as most used oxidants tert-butyl hydroperoxide, and hydrogen peroxide and mild reaction conditions. The reaction mechanism proceeds through the generation of an intermediate reactive metal–oxygen species by catalyst-oxidant interactions. Overall, most of the studies highlight the synergetic effects among the metal and support for the activity and selectivity enhancement.

scholarly journals Preparation of iron(IV) nitridoferrate Ca4FeN4 through azide-mediated oxidation under high-pressure conditions

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Simon D. Kloß ◽  
Arthur Haffner ◽  
Pascal Manuel ◽  
Masato Goto ◽  
Yuichi Shimakawa ◽  
...  
Keyword(s):  
High Pressure ◽  
Transition Metal Nitrides ◽  
Oxidative Potential ◽  
Antiferromagnetic Ordering ◽  
Chemical Inertness ◽  
High Thermodynamic Stability ◽  
Li Ion ◽  
Pressure Synthesis ◽  
Ternary Nitride ◽  
Mediated Oxidation

AbstractTransition metal nitrides are an important class of materials with applications as abrasives, semiconductors, superconductors, Li-ion conductors, and thermoelectrics. However, high oxidation states are difficult to attain as the oxidative potential of dinitrogen is limited by its high thermodynamic stability and chemical inertness. Here we present a versatile synthesis route using azide-mediated oxidation under pressure that is used to prepare the highly oxidised ternary nitride Ca4FeN4 containing Fe4+ ions. This nitridometallate features trigonal-planar [FeN3]5− anions with low-spin Fe4+ and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterised by neutron diffraction, 57Fe-Mössbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.

TBAI Catalyzed Electrochemical C-H Bond Activation of 2-arylated-N-methoxyamides for the Synthesis of Phenanthridinones

Synlett ◽  
2021 ◽  
Author(s):  
Kripa Subramanian ◽  
Subhash L. Yedage ◽  
Kashish Sethi ◽  
Bhalchandra M. Bhanage
Keyword(s):  
Electrochemical Method ◽  
Bond Activation ◽  
Supporting Electrolyte ◽  
Bioactive Compound ◽  
Reaction Conditions ◽  
Redox Catalyst ◽  
Synthetic Utility ◽  
One Step ◽  
Constant Potential

An electrochemical method for the synthesis of phenanthridinones via constant potential electrolysis (CPE) mediated by <i>n</i>-Bu<sub>4</sub>NI (TBAI) has been reported. The protocol is metal and oxidant free and proceeds with 100% current efficiency. Here TBAI plays the dual role of the redox catalyst as well as supporting electrolyte. The intramolecular C-H activation proceeds under mild reaction conditions and short reaction time via electrochemically generated amidyl radicals. The reaction has been scaled up to gram level showing its practicability and the synthetic utility and applicability of the protocol has been demonstrated by the direct one-step synthesis of the bioactive compound Phenaglaydon.

scholarly journals Design of bifunctional quaternary phosphonium salt catalysts for CO2 fixation reaction with epoxides under mild conditions

2016 ◽  
Vol 18 (17) ◽  
pp. 4611-4615 ◽  
Author(s):  
Shiyao Liu ◽  
Naoki Suematsu ◽  
Keiji Maruoka ◽  
Seiji Shirakawa
Keyword(s):  
Co2 Fixation ◽  
Phosphonium Salt ◽  
Cyclic Carbonates ◽  
Efficient Synthesis ◽  
Reaction Conditions ◽  
Mild Conditions ◽  
Phosphonium Iodide ◽  
Fixation Reaction ◽  
Quaternary Phosphonium Salt

An efficient synthesis of cyclic carbonates from epoxides and CO2 under mild reaction conditions was achieved via the use of a designed bifunctional quaternary phosphonium iodide catalyst.

scholarly journals Cross‐Coupling of Aryl/Alkenyl Pivalates with Organozinc Reagents through Nickel‐Catalyzed CO Bond Activation under Mild Reaction Conditions

2009 ◽  
Vol 48 (8) ◽  
pp. 1351-1351
Author(s):  
Bi‐Jie Li ◽  
Yi‐Zhou Li ◽  
Xing‐Yu Lu ◽  
Jia Liu ◽  
Bing‐Tao Guan ◽  
...  
Keyword(s):  
Bond Activation ◽  
Cross Coupling ◽  
Reaction Conditions ◽  
Organozinc Reagents

scholarly journals Visible Light Photochemical Reactions for Nucleic Acid-Based Technologies

Molecules ◽  
2021 ◽  
Vol 26 (3) ◽  
pp. 556
Author(s):  
Bonwoo Koo ◽  
Haneul Yoo ◽  
Ho Jeong Choi ◽  
Min Kim ◽  
Cheoljae Kim ◽  
...  
Keyword(s):  
Nucleic Acid ◽  
Nucleic Acids ◽  
Visible Light ◽  
Chemical Reactions ◽  
Chemical Biology ◽  
Photochemical Reactions ◽  
Reaction Conditions ◽  
Promising Tool ◽  
Recent Developments ◽  
Visible Light Driven

The expanding scope of chemical reactions applied to nucleic acids has diversified the design of nucleic acid-based technologies that are essential to medicinal chemistry and chemical biology. Among chemical reactions, visible light photochemical reaction is considered a promising tool that can be used for the manipulations of nucleic acids owing to its advantages, such as mild reaction conditions and ease of the reaction process. Of late, inspired by the development of visible light-absorbing molecules and photocatalysts, visible light-driven photochemical reactions have been used to conduct various molecular manipulations, such as the cleavage or ligation of nucleic acids and other molecules as well as the synthesis of functional molecules. In this review, we describe the recent developments (from 2010) in visible light photochemical reactions involving nucleic acids and their applications in the design of nucleic acid-based technologies including DNA photocleaving, DNA photoligation, nucleic acid sensors, the release of functional molecules, and DNA-encoded libraries.

Nitroxides as reaction intermediates

1982 ◽  
Vol 60 (12) ◽  
pp. 1414-1420 ◽  
Author(s):  
Hans Gunter Aurich
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Isopropyl Alcohol ◽  
High Reactivity ◽  
Reaction Intermediates ◽  
Reaction Products ◽  
Nitronyl Nitroxide ◽  
Reaction Conditions ◽  
Spin Resonance ◽  
Secondary Reactions

Vinyl nitroxides 4 are obtained by oxidation of the nitrones 3, as was shown by esr studies and by identification of the reaction products. The formation of 4d–f is even observed in oxidation of the hydroxylamines 1d–f, nitroxides 2d–f and nitrones 3d–f being the intermediates. The high reactivity of the vinyl nitroxides 4 at their β-position is illustrated by the reactions of 4a with various compounds affording the nitroxides 7–10, respectively. Compound 4c reacts with its precursor 3c to give 11, 12, or 13, depending on the reaction conditions. From oxidation of 3a, c, and e the dimerization products 5a, c, and e, respectively, could be isolated. Whereas further oxidation of 5d yields 6d, the acyl nitroxides 14a and c are formed in the oxidation of 5a and c, respectively.The formation of quinone 23 in the reaction of 2-methyl-2-nitrosopropane with potassium tert-butoxide in isopropyl alcohol in the presence of oxygen is discussed. The nitroxide 20 has been detected in the reaction mixture. Imines 24 react with nitrosobenzene giving nitroxides 26. These are further oxidized by nitrosobenzene to afford nitrones 27. Whereas 27a and b could be isolated, 27c and d undergo further reaction yielding the diimines 30c and d along with dinitrone 29.The formation and reactions of imino nitroxides 31 and of the nitronyl nitroxide 41 are discussed. Electron spin resonance studies revealed the high reactivity of the imidazolyl-1,3-dioxides 46 and the imidazolyl-1-oxides 50, which easily form radicals 47–49 and 51, respectively, which are derived from secondary reactions.

Research into Thermocatalytic Propane-to-Propylene Synthesis Using Iron-Containing Composite Carbon Materials

2021 ◽  
pp. 100-114
Author(s):  
E.B. Markova ◽  
A.G. Cherednichenko ◽  
L.S. Akhmedova ◽  
Yu.M. Averina ◽  
Yu.M. Serov
Keyword(s):  
Carbon Nanotubes ◽  
Iron Oxide ◽  
Service Life ◽  
Oil And Gas ◽  
Carbon Matrix ◽  
Propane Conversion ◽  
Reaction Products ◽  
Chemical Production ◽  
Catalytic Systems ◽  
Propylene Selectivity

The development of modern thermocatalytic technologies for processing oil and gas raw materials is one of the promising areas for the advancement of chemical production. New highly efficient catalytic systems with the required technical characteristics and long service life play an essential role in solving these issues. The paper focuses on obtaining propylene by selective propane dehydrogenation. In the course of the experiments, composite iron-containing catalysts were synthesized, in which the active component is iron oxide in combination with an inert carbon matrix. FAS activated carbon and carbon nanotubes were used as the matrix. As a result of the synthesis on the catalyst surface it was possible to obtain catalytic centers that transfer electrons by changing the degree of iron oxidation when converting the starting materials into the target reaction products. Findings of research show that the obtained iron-containing catalysts significantly increase the efficiency of the process in comparison with the efficiency of thermal cracking of propane. Thus, the Fe3+/FAS catalyst showed a conversion rate of the initial reagent of 68 % and a propylene selectivity of about 42 %. Further transition to catalytic systems based on singlelayer and double-layer carbon nanotubes modified with iron oxide (Fe3+/CNTI and Fe3+/CNTII) made it possible to obtain propane conversion up to 37--40 % with a decrease in propylene selectivity to 29--30 %. Studies of the service life of the synthesized catalytic systems and the possibility of their regeneration show that, with account for the regeneration, the activity of the catalysts and the main technical characteristics of the propane-to-propylene cracking process remain unchanged for 10 working cycles

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