We have developed radical C-glycosylation using photoexcitable unprotected glycosyl borate. The direct excitation of glycosyl borate under visible light irradiation enabled the generation of anomeric radical without any photoredox catalysts. The in situ generated anomeric radical was applicable to the radical addition such as Giese-type addition and Minisci-type reaction to introduce alkyl and heteroaryl groups at the anomeric position. In addition, the radical-radical coupling between the glycosyl borate and acyl imidazolide provided unprotected acyl C-glycosides.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.202402256 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cage-Shaped Borate Catalysts Bearing Precisely Controlled Lewis Acidity and Their Application in Glycosylations.
J Org Chem
November 2024
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Cage-shaped borates, whose Lewis acidity can be precisely modulated by the structural attributes of the triphenolic ligands, were employed as catalysts for glycosylation. Each cage-shaped borate displayed distinctive reactivity; thus, screening of the borate catalysts enabled controllable activation of glycosyl fluorides under mild conditions. Practical glycosylation was achieved by fine-tuning the Lewis acidity tailored to the substrate reactivity, thereby providing a versatile method applicable to the synthesis of complex glycans.
View Article and Find Full Text PDFRadical C-Glycosylation Using Photoexcitable Unprotected Glycosyl Borate.
Chemistry
September 2024
Institute for Chemical Research Kyoto University, 611-0011, Gokasho, Uji, Kyoto, Japan.
We have developed radical C-glycosylation using photoexcitable unprotected glycosyl borate. The direct excitation of glycosyl borate under visible light irradiation enabled the generation of anomeric radical without any photoredox catalysts. The in situ generated anomeric radical was applicable to the radical addition such as Giese-type addition and Minisci-type reaction to introduce alkyl and heteroaryl groups at the anomeric position.
View Article and Find Full Text PDFGolgi-localized APYRASE 1 is critical for Arabidopsis growth by affecting cell wall integrity under boron deficiency.
Physiol Plant
April 2024
National Key Laboratory of Crop Genetic Improvement, Huazhong Agricultural University, Wuhan, China.
Many nucleoside triphosphate-diphosphohydrolases (NTPDases/APYRASEs, APYs) play a key role in modulating extracellular nucleotide levels. However, the Golgi-localized APYs, which help control glycosylation, have rarely been studied. Here, we identified AtAPY1, a gene encoding an NTPDase in the Golgi apparatus, which is required for cell wall integrity and plant growth under boron (B) limited availability.
View Article and Find Full Text PDFStereoselective Synthesis of -Glycosides with Borate Acceptors.
J Org Chem
August 2023
Hubei Key Laboratory of Natural Products Research and Development, Key Laboratory of Functional Yeast (China National Light Industry), College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. China.
Borate esters have been applied widely as coupling partners in organic synthesis. However, the direct utilization of borate acceptors in -glycosylation with glycal donors remains underexplored. Herein, we describe a novel -glycosylation resulting in the formation of 2,3-unsaturated -glycosides and 2-deoxy -glycosides mediated by palladium and copper catalysis, respectively.
View Article and Find Full Text PDFBiased Borate Esterification during Nucleoside Phosphorylase-Catalyzed Reactions: Apparent Equilibrium Shifts and Kinetic Implications.
Angew Chem Int Ed Engl
May 2023
Institute for Biochemistry, Biotechnology and Bioinformatics, Technische Universität Braunschweig, Spielmannstraße 7, 38106, Braunschweig, Germany.
Biocatalytic nucleoside (trans-)glycosylations catalyzed by nucleoside phosphorylases have evolved into a practical and convenient approach to the preparation of modified nucleosides, which are important pharmaceuticals for the treatment of various cancers and viral infections. However, the obtained yields in these reactions are generally determined exclusively by the innate thermodynamic properties of the nucleosides involved, hampering the biocatalytic access to many sought-after target nucleosides. We herein report an additional means for reaction engineering of these systems.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!