Simple Carboxylic Acids Research Articles

Participation of strong charge-assisted hydrogen bonds in interactions of dissolved organic matter represented by Suwannee River Humic Acid

Terrestrial dissolved organic matter (DOM) plays critical roles in many biotic and abiotic environmental reactions as well as in water treatment. Its structure is therefore of great interest. We examined dissolved Suwannee River Humic Acid (HA) to probe the potential participation of exceptionally strong, negative charge-assisted hydrogen bonds, (−)CAHB, in DOM cohesion and interaction with small weak acids using high performance size exclusion chromatography (HPSEC), transmission electron microscopy, zeta-pH curves, and pH drift experiments. The results support a previously proposed two-tier state of aggregation, in which tightly-knit primary particles (≤ ∼10 kDa) form larger secondary aggregates (up to micrometer in size). Evidence for (−)CAHB is gained through zeta potential changes and pH drift experiments. The primary particles interact with (−)CAHB-capable solutes (simple carboxylic acids and phosphate) but not (−)CAHB-incapable solutes. We identified disruption of intra-segmental and inter-molecular (−)CAHB leading to swelling and disaggregation, as well as formation of nouveau (−)CAHB with free groups on HA. The effects were solute-concentration dependent and greater at pH 5 than pH 6, consistent with CAHB theory. Phosphate induced the greatest shifts in the HPSEC molecular size distribution curves. The shifts were unaffected by prior stripping of innate polyvalent metals. We conclude that the (−)CAHB contributes to the cohesion of DOM, affecting its size and charge, and provides a means by which weak acid pollutants, nutrients, and natural compounds can interact with DOM. Such interactions have implications for the behavior of DOM in the environment, the fate and transport of anthropogenic pollutants, and the roles DOM play in water treatment technologies.

Electrophotochemical metal-catalyzed synthesis of alkylnitriles from simple aliphatic carboxylic acids.

We report a practical and sustainable electrophotochemical metal-catalyzed protocol for decarboxylative cyanation of simple aliphatic carboxylic acids. This environmentally friendly method features easy availability of substrates, broad functional group compatibility, and directly converts a diverse range of aliphatic carboxylic acids including primary and tertiary alkyl acids into synthetically versatile alkylnitriles without using chemical oxidants or costly cyanating reagents under mild reaction conditions.

Environmental system analysis on formic acid synthesis from captured CO2 and green H2 using life cycle assessment methodology

Abstract Hydrogen (H2) is highly promising as an alternative energy source because it does not emit CO2 when used; thus, H2 utilization is a potential solution to fossil fuel depletion and global warming. In our previous studies, green H2 was developed through biomass pyrolysis. Meanwhile, the development of carbon dioxide capture utilization technologies to recycle CO2 gas from fossil fuel is being considered. Moreover, formic acid (FA) synthesis is among the candidate procedures for utilizing captured CO2. FA is a vital chemical substance with numerous industrial applications. As the simplest carboxylic acid, FA produces various chemical products. The demand for FA will continue to increase, mainly due to recent technological advancements in fuel cells and renewable energy. The primary pathway for FA synthesis involves the hydrolysis of fossil fuel–derived formic acid methyl. In this study, we investigated FA synthesis using CO2 from fossil fuel and green H2 from biomass as raw materials. Subsequently, we evaluated the environmental impact of the synthesized FA compared with the conventional fossil fuel–derived FA by applying the life cycle assessment methodology. The evaluation focuses on Japan, aiming to reduce environmental impact as an evaluation metric while considering the constraints on CO2 emissions and H2 production scale. Furthermore, we sought to identify the conditions that would reduce the environmental impact of FA synthesis.

Simplified Modular Access to Enantiopure 1,2-Aminoalcohols via Ni-Electrocatalytic Decarboxylative Arylation.

Chiral aminoalcohols are omnipresent in bioactive compounds. Conventional strategies to access this motif involve multiple-step reactions to install the requisite functionalities stereoselectively using conventional polar bond analysis. This study reveals that a simple chiral oxazolidine-based carboxylic acid can be readily transformed to substituted chiral aminoalcohols with high stereochemical control by Ni-electrocatalytic decarboxylative arylation. This general, robust, and scalable coupling can be used to synthesize a variety of medicinally important compounds, avoiding protecting and functional group manipulations, thereby dramatically simplifying their preparation.

Electrochemical Ni‐Catalyzed Decarboxylative C(sp3)−N Cross‐Electrophile Coupling

AbstractA new electrochemical transformation is presented that enables chemists to couple simple alkyl carboxylic acid derivatives with an electrophilic amine reagent to construct C(sp3)−N bond. The success of this reaction hinges on the merging of cooperative electrochemical reduction with nickel catalysis. The chemistry exhibits a high degree of practicality, showcasing its wide applicability with 1°, 2°, 3° carboxylic acids and remarkable compatibility with diverse functional groups, even in the realm of late‐stage functionalization. Furthermore, extensive mechanistic studies have unveiled the engagement of alkyl radicals and iminyl radicals; and elucidated the multifaceted roles played by iPr2O, Ni catalyst, and electricity.

Electrochemical Ni-Catalyzed Decarboxylative C(sp3 )-N Cross-Electrophile Coupling.

A new electrochemical transformation is presented that enables chemists to couple simple alkyl carboxylic acid derivatives with an electrophilic amine reagent to construct C(sp3 )-N bond. The success of this reaction hinges on the merging of cooperative electrochemical reduction with nickel catalysis. The chemistry exhibits a high degree of practicality, showcasing its wide applicability with 1°, 2°, 3° carboxylic acids and remarkable compatibility with diverse functional groups, even in the realm of late-stage functionalization. Furthermore, extensive mechanistic studies have unveiled the engagement of alkyl radicals and iminyl radicals; and elucidated the multifaceted roles played by i Pr2 O, Ni catalyst, and electricity.

Pyridine-borane complex-catalysed thioesterification: the direct conversion of carboxylic acids to thioesters.

Thioesters are a common class of biologically active fragments and synthetically useful building blocks. An attractive synthetic approach would be to use simple and bench-stable carboxylic acids as a coupling partner. Herein, we present a 4-bromo pyridine-borane complex as a catalyst for the direct coupling of carboxylic acids with thiols. A wide range of thioesters with good functional group compatibility could be prepared via this metal-free approach. The merit of this strategy is exemplified by the modification of carboxylic acid-containing drugs.

Switchable Decarboxylation by Energy- or Electron-Transfer Photocatalysis.

Kolbe dimerization and Hofer-Moest reactions are well-investigated carboxylic acid transformations, wherein new carbon-carbon and carbon-heteroatom bonds are constructed via electrochemical decarboxylation. These transformations can be switched by choosing an electrode that allows control of the reactive intermediate, such as carbon radical or carbocation. However, the requirement of a high current density diminishes the functional group compatibility with these electrochemical reactions. Here, we demonstrate the photocatalytic decarboxylative transformation of activated carboxylic acids in a switchable and functional group-compatible manner. We discovered that switching between Kolbe-type or Hofer-Moest-type reactions can be accomplished with suitable photocatalysts by controlling the reaction pathways: energy transfer (EnT) and single-electron transfer (SET). The EnT pathway promoted by an organo-photocatalyst yielded 1,2-diarylethane from arylacetic acids, whereas the ruthenium photoredox catalyst allows the construction of an ester scaffold with two arylmethyl moieties via the SET pathway. The resulting radical intermediates were coupled to olefins to realize multicomponent reactions. Consequently, four different products were selectively obtained from a simple carboxylic acid. This discovery offers new opportunities for selectively synthesizing multiple products via switchable reactions using identical substrates with minimal cost and effort.

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids.

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis of alkenes with all substitution patterns has been accomplished by means of Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl acids as the limiting reagents and exhibit a broad scope with respect to both coupling partners. Notably, simple primary alkyl carboxylic acids could be readily engaged as carbon-centered radical precursors in the reaction. This new alkenylation protocol has been successfully demonstrated in direct modification of naturally occurring complex acids and is amenable to the enantioselective decarboxylative alkenylation of arylacetic acid. Mechanistic studies, including a series of controlled experiments and cyclic voltammetry data, allow us to probe the key intermediates and the pathway of the reaction.

The Intrinsic Barrier Width and Its Role in Chemical Reactivity.

Chemical reactions are in virtually all cases understood and explained on the basis of depicting the molecular potential energy landscape, i.e., the change in atomic positions vs the free-energy change. With such landscapes, the features of the reaction barriers solely determine chemical reactivities. The Marcus dissection of the barrier height (activation energy) on such a potential into the thermodynamically independent (intrinsic) and the thermodynamically dependent (Bell-Evans-Polanyi) contributions successfully models the interplay of reaction rate and driving force. This has led to the well-known and ubiquitously used reactivity paradigm of "kinetic versus thermodynamic control". However, an analogous dissection concept regarding the barrier width is absent. Here we define and outline the concept of intrinsic barrier width and the driving force effect on the barrier width and report experimental as well as theoretical studies to demonstrate their distinct roles. We present the idea of changing the barrier widths of conformational isomerizations of some simple aromatic carboxylic acids as models and use quantum mechanical tunneling (QMT) half-lives as a read-out for these changes because QMT is particularly sensitive to barrier widths. We demonstrate the distinct roles of the intrinsic and the thermodynamic contributions of the barrier width on QMT half-lives. This sheds light on resolving conflicting trends in chemical reactivities where barrier widths are relevant and allows us to draw some important conclusions about the general relevance of barrier widths, their qualitative definition, and the consequences for more complete descriptions of chemical reactions.

Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity.

A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer-Moest process with unprecedented chemoselectivity.

Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity**

AbstractA mild, scalable (kg) metal‐free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer‐Moest process with unprecedented chemoselectivity.

Rapid chemical recycling of waste polyester plastics catalyzed by recyclable catalyst

Waste plastics are serious environmental threats due to their low degradability and low recycling rate. Rapid and efficient waste plastics recycling technologies are urgently demanded for a sustainable future. Herein, we report a rapid, closed-loop, and streamlined process to convert polyesters such as poly(ethylene terephthalate) (PET) back to its purified monomers. Using trifluoromethanesulfonic acid or metal triflates as the recyclable catalyst, polyesters such as PET can be completely depolymerized by simple carboxylic acids within 1 h. By coupling this acidolysis with a subsequent hydrogenolysis process, the consumed carboxylic acid was recovered and the closed-loop of PET depolymerization could be established. All catalysts and depolymerization agents are fully recycled while only PET and hydrogen are consumed.

Safety Assessment of Polyglyceryl Fatty Acid Esters as Used in Cosmetics.

The Expert Panel for Cosmetic Ingredient Safety (Panel) assessed the safety of 274 polyglyceryl fatty acid esters. Each of the esters in this group is a polyether comprising 2 to 20 glyceryl residues, end-capped by esterification with simple carboxylic acids, such as fatty acids. Most of these ingredients are reported to function in cosmetics as skin-conditioning agents and/or surfactants. The Panel reviewed the available data and considered conclusions from their relevant previous reports, and determined that these ingredients are safe in cosmetics in the present practices of use and concentration described in this safety assessment when formulated to be non-irritating.

A Catalytic Method for the Enantioselective Synthesis of α‐Quaternary Ketones, α‐Ketoesters and Aldehydes

AbstractA practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α‐quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl‐substituted ketone and aldehyde products in 25–94 % yield and 90 : 10 to >99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.

A Catalytic Method for the Enantioselective Synthesis of α-Quaternary Ketones, α-Ketoesters and Aldehydes.

A practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α-quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl-substituted ketone and aldehyde products in 25-94 % yield and 90 : 10 to >99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.

Surface-Templated Glycopolymer Nanopatterns Transferred to Hydrogels for Designed Multivalent Carbohydrate-Lectin Interactions across Length Scales.

Multivalent interactions between carbohydrates and proteins enable a broad range of selective chemical processes of critical biological importance. Such interactions can extend from the macromolecular scale (1-10 nm) up to much larger scales across a cell or tissue, placing substantial demands on chemically patterned materials aiming to leverage similar interactions in vitro. Here, we show that diyne amphiphiles with carbohydrate headgroups can be assembled on highly oriented pyrolytic graphite (HOPG) to generate nanometer-resolution carbohydrate patterns, with individual linear carbohydrate assemblies up to nearly 1 μm, and microscale geometric patterns. These are then photopolymerized and covalently transferred to the surfaces of hydrogels. This strategy suspends carbohydrate patterns on a relatively rigid polydiacetylene (persistence length ∼ 16 nm), exposed at the top surface of the hydrogel above the bulk pore structure. Transferred patterns of appropriate carbohydrates (e.g., N-acetyl-d-glucosamine, GlcNAc) enable selective, multivalent interactions (KD ∼ 40 nM) with wheat germ agglutinin (WGA), a model lectin that exhibits multivalent binding with appropriately spaced GlcNAc moieties. WGA binding affinity can be further improved (KD ∼ 10 nM) using diacetylenes that shift the polymer backbone closer to the displayed carbohydrate, suggesting that this strategy can be used to modulate carbohydrate presentation at interfaces. Conversely, GlcNAc-patterned surfaces do not induce specific binding of concanavalin A, and surfaces patterned with glucuronic acid, or with simple carboxylic acid or hydroxyl groups, do not induce WGA binding. More broadly, this approach may have utility in designing synthetic glycan-mimetic interfaces with features from molecular to mesoscopic scales, including soft scaffolds for cells.

Electrophotochemical Metal-Catalyzed Decarboxylative Coupling of Aliphatic Carboxylic Acids.

An electrophotochemical dual metal-catalyzed protocol for decarboxylative arylation of simple aliphatic carboxylic acids with aryl halides is reported. The relative stabilities of catalytically active metal complexes simultaneously generated at anode and cathode are the key design elements for the success of this convergent paired electrolysis. This new electrophotocatalytic method is mild, robust, and most importantly, capable of accommodating simple primary aliphatic acids including acetic acid - ubiquitous and variegated structural motifs yet remain oddly challenging substrates - directly as native functional groups for decarboxylative C(sp2 )-C(sp3 ) bond formation.

Intermolecular Hydrogen Bonding in Alpha-Hydroxy Carboxylic Acids Crystals: Connectivity, Synthons, Supramolecular Motifs

Synthon theory underlies the analysis and empirical prediction of the crystal structure. Supramolecular synthons (SMSs) formed by intermolecular hydrogen bonds, such as carboxylic R22(8) and C11(4) and alcoholic C11(2) ones, are among the most popular. The subject of this publication is the identification of specific synthons in alpha-hydroxycarboxylic acids (AHAs) crystals, in which carboxyl and alcohol fragments are present simultaneously. A series of 11 single-enantiomeric and racemic crystals of substituted lactic acids, the simplest chiral AHA family, were prepared and studied by the single-crystal X-ray diffraction (SC-XRD) method. Advanced analysis of our own and published (Cambridge Structural Database) data on the 33 crystal structures of lactic and achiral AHAs of diverse structures revealed that their supramolecular organization differs significantly from that of simple carboxylic acids. We found that in AHA crystals, hydrogen bonds RC(O)O−H···O(H)−C(R′R′′)C(O)OH (in our notation HB 12) and O=C(OH)C(R′R′′)−O−H···O=C(OH)R′ (HB 23) predominate. The frequency of intermolecular hydrogen bonds is interconnected with the frequency of SMSs. Thus, the synthons mentioned above occur but do not dominate in AHA crystals. Linear synthons C22(6):12/23 and cyclic synthons R22(10):23/23 and R33(11):12/23/23 are most often implemented. An essential role in the choice of cyclic synthons is played by the chiral characteristics of the sample.

The structure of a polyketide synthase bimodule core.

Polyketide synthases (PKSs) are predominantly microbial biosynthetic enzymes. They assemble highly potent bioactive natural products from simple carboxylic acid precursors. The most versatile families of PKSs are organized as assembly lines of functional modules. Each module performs one round of precursor extension and optional modification, followed by directed transfer of the intermediate to the next module. While enzymatic domains and even modules of PKSs are well understood, the higher-order modular architecture of PKS assembly lines remains elusive. Here, we visualize a PKS bimodule core using cryo–electron microscopy and resolve a two-dimensional meshwork of the bimodule core formed by homotypic interactions between modules. The sheet-like organization provides the framework for efficient substrate transfer and for sequestration of trans-acting enzymes required for polyketide production.