One-step synthesis of 2,5-diformylfuran from monosaccharides by using lanthanum(III) triflate, sulfur, and DMSO.

Chem Commun (Camb)

Department of Organic Chemistry, Faculty of Chemistry, University of Science, Ho Chi Minh City, 721337, Vietnam. and Vietnam National University-Ho Chi Minh City (VNU-HCM), 721337, Vietnam.

Published: October 2020

AI Article Synopsis

  • The study details a simple and direct method for producing 2,5-diformylfuran from glucose and fructose using lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide.
  • The method involves a one-step dehydration/oxidation of fructose that results in high yield and selectivity for the target product.
  • The authors also discuss the mechanism, scalability, and techniques for separating the product, highlighting its eco-friendly nature for large-scale applications.

Article Abstract

The combination of lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide prompted a facile, direct preparation of 2,5-diformylfuran from glucose and fructose. The one-step dehydration/oxidation of fructose afforded 2,5-diformylfuran in an excellent yield with high selectivity. The proposed mechanism, large-scale synthesis, and product separation were presented. This approach represents a straightforward and eco-friendly pathway, which can be applied in the large-scale production of 2,5-diformylfuran from fructose.

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http://dx.doi.org/10.1039/d0cc05582dDOI Listing

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Article Synopsis
  • The study details a simple and direct method for producing 2,5-diformylfuran from glucose and fructose using lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide.
  • The method involves a one-step dehydration/oxidation of fructose that results in high yield and selectivity for the target product.
  • The authors also discuss the mechanism, scalability, and techniques for separating the product, highlighting its eco-friendly nature for large-scale applications.
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Lanthanum-Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent.

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June 2019

Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, 08193, Bellaterra (Cerdanyola del Vallès), Spain.

A highly enantioselective catalytic method for the synthesis of quaternary α-trifluoromethyl derivatives of 3-oxo esters is described. The reaction uses lanthanum(III) triflate and chiral PyBOX-type C -symmetric ligands to generate intermediate La complexes that incorporate an enolate moiety of the starting 3-oxo ester and the trifluoromethylation transfer reagent. The enantioselectivity of the reaction stems from the efficient blockage of one of the prochiral faces of the La enolate by one unit of the C -symmetric ligand.

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Lanthanum trifluoromethanesulfonate is an effective single-component catalyst for synthesizing a variety of amides directly from esters and amines under mild conditions. Highly selective amidation of esters and amines, as well as catalyst-controlled amidation of esters, demonstrated the effectiveness of the catalyst system.

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The coordination chemistry and the volumetric properties of three representative lanthanoid(III) ions--lanthanum(III), gadolinium(III), and lutetium(III)--have been studied in three amide solvents with gradually increasing spatial demand upon coordination: N,N-dimethylformamide (dmf) < N,N-dimethylacetamide (dma) < N,N-dimethylpropionamide (dmp). Large angle X-ray scattering (LAXS) and EXAFS have been used to determine the structure of the solvated lanthanoid(III) ions in solution, further supplemented with a crystallographic study on octakis(N,N-dimethylacetamide)lanthanum(III) triflate, [La(dma)8](CF3SO3)3. The selection of ions and solvents allows an estimate of the steric congestion effects on the resulting coordination number, CN, ranging from nine for lanthanum(III) ions in dmf to seven for the smaller lutetium(III) ion in space-demanding dma.

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Tandem processes identified from reaction screening: nucleophilic addition to aryl N-phosphinylimines employing La(III)-TFAA activation.

J Am Chem Soc

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Reaction screening of nucleophilic reaction partners for addition to N-diphenylphosphinylimines employing lanthanum(III) triflate as a catalyst and trifluoroacetic anhydride (TFAA) as an activator is reported. A number of tandem processes leading to novel chemotypes including aza-Prins/intramolecular Friedel-Crafts annulations have been identified, and both reaction scope and mechanism further investigated.

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