Acid-catalyzed Research Articles

Formate dehydrogenase activity by a Cu(II)-based molecular catalyst and deciphering the mechanism using DFT studies.

Due to the requirement to establish renewable energy sources, formic acid (FA), one of the most probable liquid organic hydrogen carriers (LOHCs), has received great attention. Catalytic formic acid dehydrogenation in an effective and environmentally friendly manner is still a challenge. The N3Q3 ligand (N3Q3 = N,N-bis(quinolin-8-ylmethyl)quinolin-8-amine) and the square pyramidal [Cu(N3Q3)Cl]Cl complex have been synthesised in this work and characterised using several techniques, such as NMR spectroscopy, mass spectrometry, EPR spectroscopy, cyclic voltammetry, X-ray diffraction and DFT calculations. This work investigates the dehydrogenation of formic acid using a molecular and homogeneous catalyst [Cu(N3Q3)Cl]Cl in the presence of HCOONa. The mononuclear copper complex exhibits catalytic activity towards the dehydrogenation of formic acid in H2O with the evolution of a 1 : 1 CO2 and H2 mixture. The activation energy of formic acid dehydrogenation was calculated to be Ea = 86 kJ mol-1, based on experiments carried out at various temperatures. The Gibbs free energy was found to be 82 kJ at 298 K for the decomposition of HCOOH. The DFT studies reveal that [Cu(N3Q3)(HCOO-)]+ undergoes an uphill process of rearrangement followed by decarboxylation to generate [Cu(N3Q3)(H-)]+. The initial uphill step for forming a transition state is the rate-determining step. The [Cu(N3Q3)(H-)]+ follows an activated state in the presence of HCOOH to liberate H2 and generate the [Cu(N3Q3)(OH2)]2+.

Enantioselective synthesis of α-tetrasubstituted (1-indolizinyl) (diaryl)-methanamines via chiral phosphoric acid catalysis.

An enantioselective Friedel-Crafts reaction of cyclic α-diaryl N-acyl imines with indolizines catalyzed by a chiral spirocyclic phosphoric acid has been developed. The asymmetric transformation proceeds smoothly to afford α-tetrasubstituted (1-indolizinyl) (diaryl)methanamines in good yields with up to 98% ee under mild conditions.

A cryptand-like Ti-coordination compound with visible-light photocatalytic activity in CO2 storage.

A cryptand-like Ti-coordination compound, namely Ti12Cs, comprising two Ti6-salicylate cages and hosting two Cs+ ions, was synthesized by the solvothermal method. It exhibits strong visible-light absorption with an absorption band edge of 652 nm, attributed to the electron transition from salicylate ligands to Ti ions. Electrochemical impedance, visible-light transient photocurrent response, and photoluminescence spectra confirm that Ti12Cs has excellent visible-light response and charge-separation properties. Ti12Cs can be used as a heterogeneous and recyclable photocatalyst for CO2/epoxide cycloaddition, with high utilization efficiency of visible-light under mild conditions. The mechanism investigation points to a synergistic effect of photocatalysis and Lewis acid catalysis.

Hydroxy-directed peptide bond formation from α-amino acid-derived inert esters enabled by boronic acid catalysis.

A boronic acid-catalyzed peptide bond formation from α-amino acid methyl esters is described. The catalysis showed high chemoselectivity for β-hydroxy-α-amino esters, affording the peptides in high to excellent yields with high functional group tolerance. This hydroxy-directed peptide bond formation could be applicable to oligopeptide syntheses. This is the first successful example of organoboron-catalyzed peptide bond formation from α-amino acid-derived inert esters.

Theoretical insights into the enantiodivergence induced by chiral phosphoric acid catalysis with a Lewis acid for the synthesis of N-N axially chiral atropisomers.

A detailed theoretical mechanistic investigation on chiral phosphoric acid (CPA)-catalyzed Paal-Knorr reactions, in the presence and absence of a Lewis acid, for the synthesis of N-N axially chiral atropisomers is described herein. Density functional theory (DFT) studies elucidate that in the absence of a Lewis acid, CPA catalyzes both the initial cyclization and the subsequent dehydroxylation processes, ambiguously identified as the rate-determining step in the reactions. Conversely, when a Lewis acid participates in the reaction, it facilitates the second dehydroxylation process with a significantly lower energy barrier, thereby reversing the rate-determining step to the initial cyclization step. It is noteworthy that in the case of N-aminoindoles, both the S-configurational transition state TS1 in the cyclization step and TS2 in the dehydroxylation process are favourable. In contrast, for the synthesis of a bispyrrole, the R-configurational TS1 and the S-configurational TS2 are dominant. Therefore, the enantiodivergence observed is essentially induced by the reversed rate-determining steps in the absence or presence of a Lewis acid in the case of a bispyrrole. Furthermore, the non-covalent interaction (NCI) and atoms-in-molecules (AIM) analysis of the TS structures reveal that the non-covalent interactions play a pivotal role in determining the enantiodivergence observed in these reactions.

Polymer-supported strong Lewis acid phosphonium cation catalysis applied to sydnone synthesis.

Organochlorophosphonium P(V) species are strong Lewis acids deriving from a low-lying σ* orbital at P opposite to Cl. Herein, applying this strong acidity to heterogenous reactivity, we introduce polymer-supported phosphorus(V)-mediated Lewis acid catalysis. Key to this innovation is the use of a recyclable solid support Merrifield resin P(V) Lewis acid catalyst with demonstrated utility for the one-pot synthesis of sydnones. This concept of pnictogen P(V) Lewis acid catalysis is simple to apply, selective, and benefits from mild conditions with short reaction times. Further, experimental and computational findings reveal the crucial mechanistic role of phosphonium cation P(V) species in these reactions.

Diversity-oriented chiral phosphoric acid catalyzed alkylation of indolizines with aminals

This study introduces enantioselective indolizine alkylation with aminals via chiral phosphoric acid catalysis, featuring scalable, functional group-tolerant processes, enabling access to diverse C1/C3-alkylated indolizines.

Stereoselective synthesis of fissoldhimine alkaloid analogues via sequential electrooxidation and heterodimerization of ureas.

This study develops a biogenetic synthesis strategy using electrooxidation and heterodimerization of N-substituted pyrrolidine-1-carboxamides to create diverse analogues of the fissoldhimine alkaloid core. Under acidic conditions, 2-alkoxypyrrolidine-1-carboxamides from Shono oxidation formed endo-heterodimers with high yields and diastereoselectivity. Enantioselective heterodimerization using chiral phosphoric acid catalysis produced exo-heterodimers with high enantioselectivity.

Synthesis of cis-fused cyclopentenone-pyrrolidine scaffolds via sequential aza-Piancatelli and Conia-ene type reactions in one pot.

A novel one-pot protocol that enables sequential execution of an aza-Piancatelli rearrangement and a Conia-ene type reaction has been developed under Lewis acid catalysis. Here, a combination of B(C6F5)3 and Cu(OTf)2, triethylamine, and triphenylphosphine yielded a wide range of cis-fused cyclopentenone-pyrrolidine scaffolds in one pot with good yields and diastereoselectivity.

A lost piece of the puzzle of the alkane cracking mechanism: a carbanion pathway on a solid base catalyst.

The alkane cracking mechanism has been a subject of intense scrutiny, with carbonium and free radical mechanisms being two well-established pathways which correlate to solid acid catalysis and thermal cracking, respectively. However, despite an understanding of these two mechanisms, certain intricacies remain unexplored, especially when it comes to alternative reaction routes over solid base materials. This gap in the knowledge hinders optimization of the desired product selectivity of alkane cracking processes. In this work, solid superbases were first prepared by impregnation of NaNO3 on MgO. The Na/MgO catalysts were characterized by XRD, BET, XPS and CO2-TPD techniques. To investigate the role of solid base materials, propane cracking was conducted over MgO and Na/MgO. SiO2 was chosen as a representative of thermal cracking. Na/MgO showed better selectivity for light olefins than MgO or SiO2. Ethylene and light olefin selectivity could reach about 65.8% and 91.7%, respectively. Meanwhile, in terms of Na/MgO, the ratio of ethylene selectivity and propylene selectivity is greater than 2, exhibiting the advantage of selectivity for ethylene, which is obviously different from MgO and SiO2. Propane cracking over Na/MgO with different loading amounts of NaNO3 was investigated further. The conversion rates of the samples presented a "volcano curve" with increasing Na content. Furthermore, DFT calculation showed that the base-catalyzed process of the propane cracking reaction follows a carbanion mechanism. The better product distribution and stronger surface base sites can be ascribed to charge transfer arising from the loading of NaNO3.

Advancements in lewis acid catalysis for friedel-crafts acylation reactions

Advancements in lewis acid catalysis for friedel-crafts acylation reactions

Organocatalytic enantioselective (4+3) cyclization for the synthesis of spiro-fused heterocyclic compounds containing isoindolinone, oxepine and indole moieties.

A refined strategy has been developed to control the regioselective asymmetric (4+3) cyclization of α-(3-isoindolinonyl) propargylic alcohols with 2-indolylmethanols, utilizing chiral phosphoric acid catalysis. This innovative organocatalytic cyclization yields spiro isoindolinone-oxepine-fused indoles featuring a spiro-quaternary stereocenter in high yields and enantioselectivities, facilitated by the solvent of 1,1-dichloro-1-fluoroethane and the additive of hexafluoroisopropanol. Additionally, the photophysical properties of product 3k are examined, revealing bright fluorescence both in the solution and the solid state.

Nanoscale and chiral metal-organic frameworks for asymmetric reactions in water: bridging Lewis acid catalysis and biological systems.

Nowadays, stereoselective control over the sheer variety of chemical transformations benefits from the multipotency of chiral Lewis acids. Their use under biocompatible conditions has long posed a challenge because profuse amounts of biogenic nucleophiles readily deactivate them. To bridge the gap between chiral Lewis acid catalysis and biocompatible chemistry, the conversion of UiO(BPY)-type nanosized metal-organic frameworks (NMOFs) into chiral variants was herein exemplified. The combination of an elongated 2,2'-bipyridyl linker and scandium salt with a hydrophobic anion proved essential to implement traits such as robustness, biocompatibility, and catalytic activity. The catalyst could construct sufficiently hydrophobic environments sequestered within the framework, catalyzing asymmetric ring-opening reactions of meso-epoxide with low catalyst loading to afford β-amino acid alcohols in high yield (up to >99%) with high enantioselectivity (up to 88%). Most impressively, it exhibited a tolerance to the ex vivo poisoning of chiral Lewis acid catalysis by biogenic nucleophiles in sharp contrast to conventional water-compatible Lewis acids.

Nitromethane assisted Brønsted acid catalyzed regioselective halogenation of alkyl aromatics

The most prevalent strategies for preparing halogenated alkyl aromatics face one remarkable challenge: low regioselectivity. Therefore, the highly regioselective halogenation of alkyl arenes is still an unsolved problem. Herein, a highly regioselective halogenation of alkyl aromatics through nitromethane-assisted Brønsted acid catalysis is disclosed. Under the mild reaction conditions, a wide diversity of halogenated alkyl aromatics is obtained in high yields with excellent regioselectivity. The hydrogen bonding of protonic acid with the solvent nitromethane promotes this transformation.

The active site of the SGNH hydrolase-like fold proteins: Nucleophile–oxyanion (Nuc-Oxy) and Acid–Base zones

SGNH hydrolase-like fold proteins are serine proteases with the default Asp-His-Ser catalytic triad. Here, we show that these proteins share two unique conserved structural organizations around the active site: (1) the Nuc-Oxy Zone around the catalytic nucleophile and the oxyanion hole, and (2) the Acid-Base Zone around the catalytic acid and base. The Nuc-Oxy Zone consists of 14 amino acids cross-linked with eight conserved intra- and inter-block hydrogen bonds. The Acid–Base Zone is constructed from a single fragment of the polypeptide chain, which incorporates both the catalytic acid and base, and whose N- and C-terminal residues are linked together by a conserved hydrogen bond. The Nuc-Oxy and Acid-Base Zones are connected by an SHLink, a two-bond conserved interaction from amino acids, adjacent to the catalytic nucleophile and base.

Trifluoromethylthiolation of Arenes Using Lewis Acid and Lewis Base Dual Catalysis.

Incorporation of the highly lipophilic trifluoromethanesulfenyl group into bioactive molecules facilitates transport through lipid membranes, and thus, CF3S-containing compounds are important for drug discovery. Although reagents and procedures have been reported for arene trifluoromethylthiolation, methods are still required that are applicable to a diverse substrate scope and can be performed under mild conditions. Here, we describe a rapid and efficient approach for the trifluoromethylthiolation of arenes by catalytic activation of N-trifluoromethylthiosaccharin using a combination of iron(III) chloride and diphenyl selenide. This dual catalytic process allowed regioselective functionalization of a wide range of arenes and N-heterocycles under mild conditions and was used for the trifluoromethylthiolation of bioactive compounds such as tyrosine and estradiol.

Bio-versus Chemical Approaches to Produce Maltodextrin (de 9 – 12) for Potential Applications in Functional Foods and Pharmaceuticals

Maltodextrin is recognized as a food and pharmaceutical additive that is safe for direct human consumption. The physical and chemical properties of maltodextrin strongly depend on its DE (dextrose equivalent) index. Maltodextrin is a hydrolyzed product derived from starch that has gained numerous industrial applications since the last few decades. Currently, there is an increasing demand for modified starch products. Unfortunately, the relevant production process remains inefficient, leading to relatively low product quality and performance. This paper reports the results of parameterized production processes of maltodextrin with DE values ranging from 9 to 12, achieved by hydrolyzing cassava starch. Two approaches were conducted in this work, including hydrolysis with the catalysis of α-amylase enzyme and HCl acid. In the α-amylase enzyme method, various factors were investigated, such as starch content, hydrolysis time, enzyme concentration, and hydrolysis temperature. In the HCl acid method, process parameters were studied, including starch content, HCl acid concentration, reaction time, and temperature. For both approaches, the DE index of maltodextrin was selected as the objective function, and it was found to be influenced by several process conditions. Utilizing a full Design of Experiment (DoE) plan, a regression equation was developed to illustrate the influence of these factors. From the regression equation, the optimal conditions for the production of desired maltodextrin were derived and compared between the two hydrolysis methods.

Advancing Sustainable Biofuel Production from Agricultural Residues: A Comprehensive Mini-Review

Fossil fuels widely satisfy the world's energy demands; however, they are absolutely unsustainable. Rational energy management is therefore one of humanity's greatest challenges in the 21st century. The sustainable resources of energy are speculated to minimize the global environmental challenges and consequences concerning the air and water quality, greenhouse effect, acid rain, etc. Biofuels-widely regarded as "fuel of future"- are a type of sustainable fuel, extracted immediately from living matter that is most likely produced over and again. Biofuels are majorly categorized into four groups based on the types of biomasses utilized as their raw material that including food crops, agricultural and industrial wastes and algae. A significant portion of lignocellulosic biomass consists of agricultural residues, presenting an opportunity to use them as a feedstock for generating biofuels. Agricultural wastes encompass more than just residues from cultivation; they also comprise wastes generated during the processing of agricultural products, livestock management, and distribution of fruits and vegetables. This review highlights the use of agricultural residues for the production of various types of Biofuels. Agricultural residues can be pretreated and treated through a myriad number of methods, for instance, acid catalysis, anaerobic digestion, hydrothermal carbonization, simultaneous saccharification, transesterification and pyrolysis; for the production of biodiesel, biogas, hydro-char, syngas and bioethanol. Each of these methods has several benefits and drawbacks since they are all conditional on some factors. Furthermore, the following study also mentions the advantages and disadvantages of biofuel production and usage.

Immobilization of Candida rugosa lipase on optimized polyamidoamine dendrimer functionalized magnetic multiwalled carbon nanotubes for green manufacture of butyl butyrate ester

Mineral acid catalysis in Fisher-Speier esterification is hazardous and have other disadvantages. The objective of the study was immobilization of Candida rugosa lipase onto iron oxide (Fe3O4) impregnated magnetic mutiwalled carbon naotubes (MMWCNTs) using amine functionalized polyamidoamine (PAMAM) dendrimers for manufacture of butyl butyrate ester. Dendrimers were synthesized from reaction of ethyl methacrylate with varying chain length of diamines 1, 4 diaminobutane (DAB) / 1, 3 diaminopropane (DAP) / ethylene diamine (ED). The effect of aliphatic alkyl chain length (CH2) of functionalizing agents ED, DAP and DAB, and dendrimer generations on amount of terminal NH2 group, surface charge, protein loading and immobilized enzyme activities were analysed. Magnetic MWCNTs support surface modified with third generation PAMAM using ethylene diamine showed highest protein load 220.1 mg g−1 and enzymatic activity 8,276.21 U g−1 support. The immobilized enzyme particles were characterized by HRTEM, FTIR, XRD, TGA, VSM and Zeta potential analysis. The immobilized enzyme showed improvement in the dispersion, activity, stability and reusability characteristics. Maximum esterification yield 92.67 % and reuse upto 11 cycles with 65.2 % yield obtained. The immobilized preparation showed 2.3 folds esterification than free enzyme. Developed nanobiocatalyst expects to possess potential for various other applications of lipase catalysed reactions.

Enantioselective (3+2)-Annulation of β-Keto Esters with Azoalkenes towards Bicyclic Dihydropyrroles via Cooperative Palladium and Brønsted Acid Catalysis

AbstractA cooperative catalytic process through palladium and Brønsted acid activation is developed for the conjugate addition of cyclic β-keto esters to azoalkenes directly followed by hemiaminal formation upon cyclization. This transformation is enabled by utilizing chiral Pd-aqua complexes as combined Brønsted acid–base catalysts. Thus, bicyclic and highly functionalized dihydropyrroles with two contiguous quaternary stereogenic centers are formed in excellent yields as single diastereomers and with exceptional enantioselectivity.