Visible light catalysis allows the regioselective synthesis of oxazolines in high yields. The mild photosensitized manifold leverages the intermolecular formation of oxazolines with a wide functional group tolerance on both benzoyl azides and alkenes partners. Mechanistic investigations suggest the sensitization of the azide moiety as the key activation step.
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http://dx.doi.org/10.1021/acs.joc.9b00568 | DOI Listing |
ChemMedChem
December 2024
Laboratoire d'Innovation Moléculaire et Applications (LIMA), Team Bio(IN)organic & Medicinal Chemistry, UMR7042 CNRS-Université de Strasbourg-Université Haute-Alsace, European School of Chemistry, Polymers and Materials (ECPM), 25, rue Becquerel, F-67087, Strasbourg, France.
This study explores the synthesis and evaluation of novel 1,2,3-triazole-methyl-1,4-naphthoquinone hybrids, focusing on their electrochemical properties and antiparasitic efficacies against two human blood-dwelling parasites Plasmodium falciparum and Schistosoma mansoni. Using copper-catalyzed azide-alkyne cycloaddition (CuAAC), a well-established tool in click chemistry, two synthetic routes were assessed to develop α- and β-[triazole-methyl]-menadione derivatives. By optimizing the CuAAC reaction conditions, yields were significantly improved, reaching up to 94 % for key intermediates and resulting in the formation of a library of approximately 30 compounds.
View Article and Find Full Text PDFInorg Chem
October 2024
Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, Braunschweig 38106, Germany.
The thorium bipyridyl metallocene (Cp)Th(bipy) (; Cp = η-1,2,4-(MeC)CH) shows a rich reactivity toward a series of small molecules. For example, complex may act as a synthon for the (Cp)Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH), Ph ( = S, Se), elemental sulfur (S) and selenium (Se), organic azides, CS, and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones PhCO and (CH)CO, aldehydes -MePhCHO and -ClPhCHO, seleno-ketone (-MeOPh)CSe, nitriles PhCN, PhCHCN, CHCN, and -(NC)Ph, and benzoyl cyanide PhCOCN, C-C coupling occurs to furnish (Cp)Th[(bipy)(PhCO)] (), (Cp)Th[(bipy)((CH)CO)] (), (Cp)Th[(bipy)(-MePhCHO)] (), (Cp)Th[(bipy)(-ClPhCHO)] (), (Cp)Th[(bipy){(-MeOPh)CSe}] (), (Cp)Th[(bipy)(PhCN)] (), (Cp)Th[(bipy)(PhCHCN)] (), (Cp)Th[(bipy)(CHCN)] (), [(Cp)Th]{μ-(bipy)[-Ph(CN)](bipy)} (), and (Cp)Th{(bipy)[PhC(CN)O]} (), respectively.
View Article and Find Full Text PDFJ Org Chem
May 2024
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States.
The Norrish type I (α-cleavage) reaction is an excellent photochemical method for radical-pair formation in solution. However, in cryogenic matrices, the starting material typically re-forms before the radical pair diffuses apart. This study focused on N extrusion from an azido alkyl radical to prevent radical-pair recombination.
View Article and Find Full Text PDFBioconjug Chem
August 2023
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1, Canada.
A series of generation 3-5 dendrons based on a bis(2,2-hydroxymethylpropionic acid) (bis-MPA) scaffold bearing three respective lengths of linear poly(ethylene glycol) at their periphery and a dibenzocyclooctyne unit at their core was prepared. These dendrons were appended to the surface of azide-decorated α-chymotrypsin (α-CT) via strain-promoted azide-alkyne cycloaddition to yield a library of dendron-protein conjugates. These conjugates were characterized by FT-IR and NMR spectroscopy and were imaged using cryo-electron microscopy.
View Article and Find Full Text PDFJ Org Chem
June 2023
Genomics Research Center, Academia Sinica, No. 128 Academia Road, Section 2, Nankang District, Taipei 11529, Taiwan.
Regioselective functionalization of unprotected carbohydrates at a secondary OH group in the presence of primary OH groups based on the commonly used organotin-mediated reaction has been improved. We found that the preactivation of the dibutylstannylene acetal intermediate with tetrabutylammonium bromide in toluene is a key to the improved condition for the efficient, high-yielding, and regioselective tosylation, benzoylation, or benzylation of unprotected carbohydrates. The counteranion of tetrabutylammonium ion with a weak coordination ability plays a crucial role in the improved regioselective reactions.
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