CO fixation technology has gained attention as a method to effectively utilize the abundant CO in the atmosphere by converting it into useful chemicals. However, since CO is a highly stable molecule, many of the currently developed methods for chemical CO fixation require harsh conditions and reactive reagents. The establishment of efficient and sustainable processes is eagerly awaited. In this study, we investigated a biocatalytic process and achieved a carboxylation reaction under mild conditions (37 °C, 0.1 MPa CO) using a biocatalyst, NADP-malic enzyme (ME), and gaseous CO by coupling enzymatic coenzyme regeneration. We also demonstrated for the first time that the carboxylation reaction by ME proceeds not only with pyruvate, a natural substrate, but also with 2-ketoglutarate.
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http://dx.doi.org/10.1021/jacsau.4c00290 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The University of Texas at Dallas, Richardson, Texas 75080, United States.
A general streamlined strategy for the enantioselective total syntheses of the schizozygane family of natural products and related alkaloid vallesamidine is described. Specifically, a catalytic enantioconvergent cross-coupling sets the quaternary stereogenic center in a pluripotent intermediate adorned with an olefin and three orthogonal carboxylate groups, upon which the modularity of the synthesis relies. A late-stage catalytic oxidative lactamization of an alkyne is instrumental in the first-generation synthesis of the schizozygane alkaloids.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Key Laboratory of Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430073, P.R. China.
Electrochemical oxidative cross-dehydrogenative-coupling (CDC) is an ideal strategy to conduct the C3-alkoxylation of imidazo[1,2-]pyridine, but it remains a challenge owing to limitation imposed by the use of alkyl alcohols and carboxylic acids. Herein, we report a mild and efficient 2-electrode constant-potential electrolysis of imidazo[1,2-]pyridine with hexafluoroisopropanol (HFIP) to produce various imidazo[1,2-]pyridine HFIP ethers. Mechanistic studies indicated that the electrooxidation reaction might involve radical coupling and ionic reaction.
View Article and Find Full Text PDFACS Cent Sci
January 2025
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, 209 Tongshan Road, Xuzhou 221004, China.
Herein, we report a visible-light-induced charge-transfer-complex-enabled dicarboxylation and deuterocarboxylation of C=C bonds with oxalate as a masked CO source under catalyst-free conditions. In this reaction, we disclosed the first example that the tetrabutylammonium oxalate could be able to aggregate with aryl substrates via π-cation interactions to form the charge transfer complexes, which subsequently triggers the single electron transfer from the oxalic dianion to the ammonium countercation under irradiation of 450 nm bule LEDs, releasing CO and CO radical anions. Diverse alkenes, dienes, trienes, and indoles, including challenging trisubstituted olefins, underwent dicarboxylation and anti-Markovnikov deuterocarboxylation with high selectivity to access valuable 1,2- and 1,4-dicarboxylic acids as well as indoline-derived diacids and β-deuterocarboxylic acids under mild conditions.
View Article and Find Full Text PDFHeliyon
January 2025
Department of Food Science and Technology, Faculty of Agriculture, Ferdowsi University of Mashhad, Mashhad, Iran.
The applicability of cellulose and its derivatives is greatly depends on their attributes such as aspect ratio, morphology, surface chemistry, crystallinity, as well as their thermal and mechanical properties. However, these attributes can alter according to the utilized raw material, size classifications, extraction techniques, or fibrillation methods. Among these, the effect of raw material particle size on cellulose properties has received limited attention in scientific studies.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Institute of Condensed Matter and Nanosciences, Molecules Solids and Reactivity (IMCN/MOST), Université Catholique de Louvain, Bâtiment Lavoisier, Pl. Louis Pasteur, 1, bte 3. 1348, Louvain La Neuve, Belgium.
The present study describes the use of the di--butyl dicarbonate (BocO)/4-(,-dimethylamino)pyridine (DMAP) system for the amidation of carboxylic acids under neat conditions without heating. A set of carboxylic acids was explored, such as non-steroidal anti-inflammatory drugs (NSAIDs), fatty acids and protected prolines in the presence of aromatic, benzylic and aliphatic amines as nucleophilic partners. The scope of this easy approach was extended to the preparation of thirty-two diverse carboxylic amides, which were recovered with isolated yields varying from moderate to excellent.
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