We designed and synthesized a ureido-linked zinc bisporphyrinate [Zn2(UBis)]. CD spectra show that this zinc bisporphyrinate has the ability to sense the chirality of chiral carboxylic acids without derivatization. Our studies suggest that the phenyl ring in the linker forms π-π interactions with porphyrin planes and that the carboxylic acid is coordinated to the zinc in the host-guest complex. DFT calculations show that the bisporphyrin adopts a \"Z\"-shaped configuration, and that the ureido group forms hydrogen bonds with carboxylic acids. The combination of π-π interactions, coordination interactions and hydrogen bonding interactions leads to the chirality sensing ability of [Zn2(UBis)].

Soil alkalization is an important environmental factor limiting crop production. Despite the importance of root secretion in the response of plants to alkali stress, the regulatory mechanism is unclear. In this study, we applied a widely targeted metabolomics approach using a local MS/MS data library constructed with authentic standards to identify and quantify root exudates of wheat under salt and alkali stresses. The regulatory mechanism of root secretion in alkali-stressed wheat plants was analyzed by determining transcriptional and metabolic responses. Our primary focus was alkali stress-induced secreted metabolites (AISMs) that showed a higher secretion rate in alkali-stressed plants than in control and salt-stressed plants. This secretion was mainly induced by high-pH stress. We discovered 55 AISMs containing -COOH groups, including 23 fatty acids, 4 amino acids, 1 amino acid derivative, 7 dipeptides, 5 organic acids, 9 phenolic acids, and 6 others. In the roots, we also discovered 29 metabolites with higher levels under alkali stress than under control and salt stress conditions, including 2 fatty acids, 3 amino acid derivatives, 1 dipeptide, 2 organic acids, and 11 phenolic acids. These alkali stress-induced accumulated carboxylic acids may support continuous root secretion during the response of wheat plants to alkali stress. In the roots, RNAseq analysis indicated that 5 6-phosphofructokinase (glycolysis rate-limiting enzyme) genes, 16 key fatty acid synthesis genes, and 122 phenolic acid synthesis genes have higher expression levels under alkali stress than under control and salt stress conditions. We propose that the secretion of multiple types of metabolites with a -COOH group is an important pH regulation strategy for alkali-stressed wheat plants. Enhanced glycolysis, fatty acid synthesis, and phenolic acid synthesis will provide more energy and substrates for root secretion during the response of wheat to alkali stress.

Palladium-catalyzed enantioselective C(sp3)-H functionalization reactions has attracted considerable attention due to its ability for the synthesis of enantiomerically enriched molecules and stimulation of novel retrosynthetic disconnections. Understanding the reaction mechanism, especially the stereochemical process of the reaction, is crucial for the rational design of more efficient catalytic systems. Previously, we developed a Pd(II)/sulfoxide-2-hydroxypridine (SOHP) catalytic system for asymmetric C(sp3)-H functionalization reactions. In this study, we focused on unraveling the chemistry of chiral palladacycles involved in the Pd(II)-catalyzed enantioselective C(sp3)-H functionalization. We have isolated key palladacycle intermediates involved in the enantioselective β-C(sp3)-H arylation of carboxylic acids catalyzed by the Pd(II)/SOHP system. These palladacycles, exhibiting ligand-induced chirality, provided a significant opportunity to investigate the stereochemical process and the ligand effect in this asymmetric C-H functionalization. Our investigation provided direct evidence for the C-H palladation step as the enantioselectivity-determining step, which forms diastereomeric palladacycles that exhibited preservation of chirality in the functionalization step. DFT calculations provided insights into the chiral induction in palladacycle formation. This work highlights the value of chiral palladacycle chemistry in offering mechanistic insights into the Pd(II)-catalyzed asymmetric C(sp3)-H functionalization reactions.

Here we report the challenging O-trifluoromethylation of carboxylic acids via the formation and activation of acyloxy(phenyl)trifluoromethyl-λ3-iodanes. The method provides an easy access to various potentially valuable and hitherto elusive trifluoromethyl carboxylic esters. A remarkably wide range of substrates with commonly encountered functional groups are compatible with this reaction, including aromatic and aliphatic carboxylic acids, as well as Food and Drug Administration (FDA) approved drugs and pharmaceutically relevant molecules. The reaction mechanism and the origins of the enhanced reactivity by zinc chloride (ZnCl2) were discussed from experimental evidence and density functional theory (DFT) calculation.

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.

Carboxylic acids containing acidic groups with additional keto/hydroxyl-groups or unsaturated bond have displayed great applicability in the food, agricultural, cosmetic, textile, and pharmaceutical industries. The traditional approach for carboxylate production through chemical synthesis is based on petroleum derivatives, resulting in concerns for the environmental complication and energy crisis, and increasing attention has been attracted to the eco-friendly and renewable bio-based synthesis for carboxylate production. The efficient and specific export of target carboxylic acids through the microbial membrane is essential for high productivity, yield, and titer of bio-based carboxylates. Therefore, understanding the characteristics, regulations, and efflux mechanisms of carboxylate transporters will efficiently increase industrial biotechnological production of carboxylic acids. Several transporters from fungi have been reported and used for improved synthesis of target products. The transport activity and substrate specificity are two key issues that need further improvement in the application of carboxylate transporters. This review presents developments in the structural and functional diversity of carboxylate transporters, focusing on the modification and regulation of carboxylate transporters to alter the transport activity and substrate specificity, providing new strategy for transporter engineering in constructing microbial cell factory for carboxylate production. KEY POINTS: • Structures of multiple carboxylate transporters have been predicted. • Carboxylate transporters can efficiently improve production. • Modification engineering of carboxylate transporters will be more popular in the future.

Nowadays, nanocellulose production processes with numerous merits of green, eco-friendly, and cost-effective are in urgent need. Acidic deep eutectic solvent (ADES), as an emerging green solvent, has been widely applied in the preparation of nanocellulose over the past few years, owing to its unique advantages, including non-toxicity, low cost, easy synthesis, recyclability, and biodegradability. At present, several studies have explored the effectiveness of ADESs in nanocellulose production, particularly those based on choline chloride (ChCl) and carboxylic acids. Various acidic deep eutectic solvents have been employed, with representative ones such as ChCl-oxalic/lactic/formic/acetic/citric/maleic/levulinic/tartaric acid. Herein, we comprehensively reviewed the latest progress of these ADESs, focusing on the treatment procedures and key superiorities. In addition, the challenges and outlooks of ChCl/carboxylic acids-based DESs implementation in the fabrication of nanocellulose were discussed. Finally, some suggestions were proposed to advance the industrialization of nanocellulose, which would help for the roadmap of sustainable and large-scale production of nanocellulose.

Efficient strategies to access nitriles from common organic functionalities are highly important, given their significance in synthetic and medicinal chemistry. Although the direct transformation of carboxylic acids to nitriles have been explored for decades, there is few general and practical protocol to access nitriles from carboxylic acid precursors. Herein, an iron-catalyzed deoxynitrogenaton strategy to convert carboxylic acids into nitriles is described. This method utilizes a cyanamide as the recyclable nitrogen donor and deoxygenating reagent, operates broadly across aryl, alkenyl, and alkyl carboxylic acids, and features an easy setup without inert gas protection. The synthetic value of this method is demonstrated by application in late-stage modification of drug molecules, synthesis of a pharmaceutical structure, and scaleup reactions and downstream derivatizations.

Carboxylic acids are abundant, low cost and environmentally friendly, direct convert carboxylic acids into valued-added compounds are in high demand. Herein, we report a Rh(I) catalyzed direct decarbonylative borylation of aryl and alkyl carboxylic acid using TFFH as activator. This protocol features excellent functional-group tolerance and a broad substrate scope including natural product and drugs. A gram-scale decarbonylative borylation reaction of Probenecid is also presented. In addition, the utility of this strategy is highlighted by a one-pot decarbonylative borylation/ derivatization sequence.

The synthetic methodologies for the α-functionalization of free carboxylic acids through the enediolate intermediates are summarized in this review. In general, the enediolates could be generated in situ or transiently from free carboxylic acids with a stoichiometric or catalytic amount of protection reagents, including metal, boron, and silicon reagents. The in situ or transient generated enediolates were subsequently subjected to racemic or asymmetric reactions with various electrophiles, producing the α-functionalized free carboxylic acids in a single step. In addition, the enediolate could undergo an α-oxidation reaction with TEMPO through the radical process.