C1 Building Block Research Articles

Crucial Role of the Chaperonin GroES/EL for Heterologous Production of the Soluble Methane Monooxygenase from Methylomonas methanica MC09

Methane is a widespread energy source and can serve as an attractive C1 building block for a future bioeconomy. The soluble methane monooxygenase (sMMO) is able to break the strong C−H bond of methane and convert it to methanol. The high structural complexity, multiplex cofactors, and unfamiliar folding or maturation procedures of sMMO have hampered the heterologous production and thus biotechnological applications. Here, we demonstrate the heterologous production of active sMMO from the marine Methylomonas methanica MC09 in Escherichia coli by co‐synthesizing the GroES/EL chaperonin. Iron determination, electron paramagnetic resonance spectroscopy, and native gel immunoblots revealed the incorporation of the non‐heme diiron centre and homodimer formation of active sMMO. The production of recombinant sMMO will enable the expansion of the possibilities of detailed studies, allowing for a variety of novel biotechnological applications.

Rh(III)-Catalyzed Synthesis of Indazolo[2,3-a]quinolines: Vinylene Carbonate as C1 and C2 Building Blocks.

A rhodium-catalyzed cyclization of azobenzenes and vinylene carbonate via C-H bond activation to construct indazolo[2,3-a]quinolines has been developed. This protocol offers an efficient method for synthesis of the titled products in good yields with broad functional group tolerance. In this reaction, three C-C bonds and C-N bond are formed in one pot, and vinylene carbonate (VC) acts as C1 and C2 synthons as well as "vinylene transfer" agent and acylation reagent in the construction of target-fused heterocycles. Moreover, the products exhibit favorable fluorescence properties, which indicate their potential application as fluorescent materials and biosensors.

Kinetically Controllable Construction of Nine-Membered Carbocycles via Pd-Catalyzed Decarboxylative Cycloaddition.

A kinetically controllable strategy toward the construction of otherwise challenging nine-membered carbocycles is reported. This Pd-catalyzed decarboxylative procedure utilizes vinyl methylene cyclic carbonates as the C5-dipole and allylidenemalononitriles as C4-building blocks. The protocol features user-friendly operations with controllable regioselectivity and generates CO2 as the sole byproduct. The formation of synthetically valuable and thermodynamically favored seven-membered carbocycles was also investigated.

Radical Esterification of Unactivated Alkenes Using Formate as Carbonyl Source.

In recent years, methyl formate has received considerable attention as an ideal and green C1 building block to synthesize carboxylic esters. However, examples of a one-step route to esters with one-carbon elongation using methyl formate as a source of methoxycarbonyl radical are still rare. Herein, we present peroxide-induced radical carbonylation of N-(2-methylallyl)benzamides with methyl formate as the precursor of methoxycarbonyl radical and RuCl3 as catalyst, affording a series of biologically valuable 4-[(methoxycarbonyl)methyl]-3,4-dihydroisoquinolinones with good tolerance and insensitivity to moisture in one pot under simple and mild conditions.

Synthesis of cyclic carbonates of different epoxides using CO2 as a C1 building block over Ag/TUD-1 mesoporous silica catalyst: A solvent free approach

Utilization of abandoned CO2 that is generated from fossil fuels and industrial sources into valuable chemicals is a smart approach for a greener future. The fixation of CO2 over epoxides and the production of cyclic carbonates is one of the popular CO2 utilization techniques. Silica supported silver nanoparticles have been used before in different important reactions like nitrophenol reduction, alcohol oxidation etc., due to the high surface area, pore size of silica and high activity of the Ag0 species. In this study, Technische Universiteit Delft -1 (TUD-1) is used as silica support for stabilizing silver nanoparticles and CO2 has been converted to cyclic carbonate under solvent less condition. The Lewis acidic nature of the silver particles have aided into the solvent-less CO2 conversion, resulting into the maximum yield of 98% at 60 °C and 1 MPa pressure.

Copper-Catalyzed [4 + 1] Annulation of Enaminothiones with Indoline-Based Diazo Compounds

A concise synthetic route to spiroindoline-fused S-heterocycles was developed through copper-catalyzed [4 + 1] annulation using enaminothiones as donor-acceptor synthons. Both 3-diazoindolin-2-imines and 3-diazooxindoles were amenable to work as effective C1 building blocks. The reaction proceeds via a copper-catalyzed cascade process involving the in situ generation of copper(I) carbene and C-S/C-C bond formation. This synthetic protocol features the use of readily available substrates, diverse substituent tolerance, and good to excellent yields.

Configurational Selectivity Study of Two-dimensional Covalent Organic Frameworks Isomers Containing D2h and C2 Building Blocks

Configurational Selectivity Study of Two-dimensional Covalent Organic Frameworks Isomers Containing D2h and C2 Building Blocks

Hydrogenation of Carbon Dioxide to Formate Using a Cadmium-Based Metal–Organic Framework Impregnated with Nanoparticles

The burning of fossil fuels to meet energy demands has increased carbon dioxide (CO2) in the atmosphere, causing global warming and associated climate change. Therefore, new materials are being developed to capture CO2 effectively, limit its impact on the environment, and store and/or utilise it as an abundant C1 building block. In this study, we investigate a cadmium(II) metal–organic framework, [Cd(bdc)(DMF)]n (MOF1), synthesised by treating benzene-1,4-dicarboxylic acid with four equivalents of [Cd(NO3)2]. MOF1 was then used to support Pd, Ni, and Pt nanoparticles in forming MOF1/Pd MOF1/Ni and MOF1/Pt, respectively. These MOF-based materials were characterised using powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR), energy-dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HR-TEM). MOF1/Pd MOF1/Ni and MOF1/Pt proved highly active in the catalytic hydrogenation of CO2 to formate selectively; in contrast, MOF1 did not hydrogenate CO2 to formate. The MOF1/Pd, MOF1/Ni, and MOF1/Pt catalysts produced formate selectively, with the highest TON of 1500 (TOF of 69 h−1) achieved using MOF1/Pd as the catalyst at 170 °C within 2 h. A formate yield of 98% was obtained, which demonstrates that the combination of nanoparticles and MOFs greatly enhances the catalytic activity of the active sites.

Palladium-catalyzed cyclization of 1-alkynyl-8-iodonaphthalene and double isocyanides for the synthesis of acenaphtho[1,2-b]pyrroles

A palladium-catalyzed formal [2 + 2 + 1] cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein. The transformation worked well to produce a series of 7 H -acenaphtho[1,2- b ]pyrrole with a broad reaction scope. Isocyanides play a dual role in the reaction. One is a C1 building block, and another is used as C1N1 component. In the process, the [2 + 2 + 1] cyclization involves imidoylation, regioselective addition of imidoylpalladium species into alkyne, double imidoylation, and another addition of the resulting imidoylpalladium species into imine bonds. A palladium-catalyzed formal [2 + 2 + 1] cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein. The transformation worked well to produce a series of 7 H -acenaphtho[1,2- b ]pyrrole with a broad reaction scope. Isocyanides play a dual role acting as C1 building block and C1N1 component.

Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes

Carbon monoxide (CO) is an indispensable C1 building block. For decades this abundant gas has been employed in hydroformylation and Pausen-Khand catalysis, amongst many related chemistries, where a single, non-coupled CO fragment is delivered to an organic molecule. Despite this, organometallic species which react with CO to yield C1 products remain rare, and are elusive for main group metal complexes. Here, we describe a range of amido-beryllium hydride complexes, and demonstrate their reactivity towards CO, in its mono-insertion into the Be-H bonds of these species. The small radius of the Be2+ ion in conjunction with the non-innocent pendant phosphine moiety of the developed ligands leads to a unique beryllium formyl complex with an ylidic P-COC fragment, whereby the carbon centre, remarkably, datively binds Be. This, alongside reactivity toward carbon dioxide, sheds light on the insertion chemistry of the Be-H bond, complimenting the long-known chemistry of the heavier Alkaline Earth hydrides.

Catalytic and Spectroscopic Properties of the Halotolerant Soluble Methane Monooxygenase Reductase from Methylomonas methanica MC09.

The soluble methane monooxygenase receives electrons from NADH via its reductase MmoC for oxidation of methane, which is itself an attractive C1 building block for a future bioeconomy. Herein, we present biochemical and spectroscopic insights into the reductase from the marine methanotroph Methylomonas methanica MC09. The presence of a flavin adenine dinucleotide (FAD) and [2Fe2S] cluster as its prosthetic group were revealed by reconstitution experiments, iron determination and electron paramagnetic resonance spectroscopy. As a true halotolerant enzyme, MmoC still showed 50 % of its specific activity at 2 M NaCl. We show that MmoC produces only trace amounts of superoxide, but mainly hydrogen peroxide during uncoupled turnover reactions. The characterization of a highly active reductase is an important step for future biotechnological applications of a halotolerant sMMO.

β-Perfluoroalkyl Peroxides as Fluorinated C3-Building Blocks for the Construction of Benzo[4,5]imidazo[1,2-a]pyridines.

An efficient and selective protocol for the synthesis of perfluoroalkyl-group-substituted benzo[4,5]imidazo[1,2-a]pyridines has been developed in which β-perfluoroalkyl peroxides act as novel fluorinated C3-building blocks to implement regioselective [3 + 3] annulation with 2-cyanomethyl benzimidazole under metal-free conditions. The application of the synthesized perfluoroalkylated BIPs as potent anticancer reagents versus the nonfluorinated ones demonstrated the biological utility of this method.

Potential Use of Microbial Enzymes for the Conversion of Plastic Waste Into Value-Added Products: A Viable Solution.

The widespread use of commercial polymers composed of a mixture of polylactic acid and polyethene terephthalate (PLA-PET) in bottles and other packaging materials has caused a massive environmental crisis. The valorization of these contaminants via cost-effective technologies is urgently needed to achieve a circular economy. The enzymatic hydrolysis of PLA-PET contaminants plays a vital role in environmentally friendly strategies for plastic waste recycling and degradation. In this review, the potential roles of microbial enzymes for solving this critical problem are highlighted. Various enzymes involved in PLA-PET recycling and bioconversion, such as PETase and MHETase produced by Ideonella sakaiensis; esterases produced by Bacillus and Nocardia; lipases produced by Thermomyces lanuginosus, Candida antarctica, Triticum aestivum, and Burkholderia spp.; and leaf-branch compost cutinases are critically discussed. Strategies for the utilization of PLA-PET’s carbon content as C1 building blocks were investigated for the production of new plastic monomers and different value-added products, such as cyclic acetals, 1,3-propanediol, and vanillin. The bioconversion of PET-PLA degradation monomers to polyhydroxyalkanoate biopolymers by Pseudomonas and Halomonas strains was addressed in detail. Different solutions to the production of biodegradable plastics from food waste, agricultural residues, and polyhydroxybutyrate (PHB)-accumulating bacteria were discussed. Fuel oil production via PLA-PET thermal pyrolysis and possible hybrid integration techniques for the incorporation of thermostable plastic degradation enzymes for the conversion into fuel oil is explained in detail.

Synthesis of 5H-Chromeno[2,3-d]pyrimidin-5-one Derivatives via Microwave-Promoted Multicomponent Reaction.

A microwave-promoted multicomponent reaction of 3-formylchromones, amines, and paraformaldehyde was achieved under catalyst-free and solvent-free conditions, delivering 5H-chromeno[2,3-d]pyrimidin-5-one derivatives in good to excellent yields via an unexpected annulation pathway, which further expanded the synthetic application of paraformaldehyde as a C1 building block.

Synthesis of Aryl Methyl Sulfides from Arysulfonyl Chlorides with Dimethyl Carbonate as the Solvent and C1 Source

AbstractA new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.

Effect of the zirconia-titania catalyst modification and CO2/CH4 ratios on CO2 coupling reaction with methane

The CO2 utilization for coupling reaction with methane for the production of C1 building block chemicals was studied. The influence of surface oxides of zirconia-titania catalysts and CO2/methane gas ratios were investigated to promote methane activation and coupling with CO2 for the production of value-added chemicals of acetic acid, ethane and ethylene. The synthesized catalysts by three impregnation methods assisted by microwave irradiation, exhibited different nanoscale crystal sizes and were characterized by various techniques of XRD, TEM, BET, NH3-TPD and H2-TPR. The anatase and tetragonal phases of ZrO2/TiO2 framework were identified and the synthesized catalysts showed an increase of surface acidity with distinct H2 reduction patterns for each catalyst as result of Zr oxide interaction with Ti oxide. Methane activation was observed and the coupling reaction produced ethane and ethylene and was affected via modified catalysts. Despite ongoing reaction, CO2 coupling reaction formulated acetic acid and consumed methyl surface species over catalyst then dimerized to form ethane and ethylene. It was found that the obtained products from CO2 coupling were altered by the variation in methane dissociation due to changing CO2/methane ratios, at which higher CO2/methane ratio (90%:10%) showed the highest methane dissociation and CO2 coupling reaction.

Effect of neutralizing agents in the preparation of succinic acid from oil palm trunk

Neutralization is an important process to control the pH required for enzymatic saccharification of pretreated biomass followed by fermentation for biochemical conversion. In this study, the production of succinic acid as a potential C4 building block was investigated by utilizing lignocellulosic biomass in the form of oil palm trunk (OPT). The effect of different neutralizing agents (NaOH, KOH and NH4OH) on the enzymatic saccharification of oxalic acid-pretreated OPT and subsequent succinic acid fermentation by Actinobacillus succinogenes ATCC 55618 was investigated. The results showed that all neutralizing agents tested were able to assist in the recovery of fermentable sugars with concentrations ranging from 38.1 to 39.6 g/L. However, during succinic acid fermentation, it was found that the soluble NH4-oxalate salt formed severely inhibited succinic acid fermentation compared to Na and K, thereby decreasing the succinic acid production from 14.0 g/L (using NaOH) to 1.0 g/L (using NH4OH). In particular, Na-and K-oxalate did not exhibit apparent inhibition for both the saccharification and fermentation processes. Hence, the choice of neutralizing reagent is essential to prevent inhibition in the preparation of succinic acid from lignocellulosic biomass.

Efficient synergistic chemical fixation of CO2 by simple metal-free organocatalysts: Mechanistic and kinetic insights

BackgroundCarbon dioxide is a versatile, non-toxic, and renewable C1 building block source to produce valuable chemicals such as cyclic carbonates. The purpose of this research is development of efficient, metal-free and affordable catalysts for cycloaddition reaction of CO2 with epoxides at mild conditions. MethodsIn the present work, a group of novel bifunctional organocatalysts consisting of different hydrogen-bond donors (HBDs) and halogen ion is simply synthesized. Under the optimized conditions, the reaction is kinetically and thermodynamically studied. Additionally, the catalytic active species are determined, and a mechanism is proposed with the help of electrospray‐ionization time‐of‐flight mass spectrometry (ESI-TOF MS). Significant findingsThe most active catalytic system is obtained by chemically interaction of 3-bromopropionic acid (BPA) with DMF at 80 °C (BPA-DMF). An excellent product yield of 98% and a high TOF value are obtained with 0.99 mol% of BPA-DMF, which is attributed to the synergistic effects of carboxyl functional groups and halide ions. The activation energy was found to be 50.75 kJ/mol. The positive value of Gibbs free activation energy (ΔG‡) and negative value of activation entropy (ΔS‡) confirm a non-spontaneous, endergonic and kinetically controlled reaction.

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)−F bonds with CO2

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)−F bonds with CO2

Desulfonylative Electrocarboxylation with Carbon Dioxide.

Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO2) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO2 as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.