The synthesis of a new amphiphilic nitrone, A, derived from a digalactosyl tris(hydroxymethyl)aminomethane bearing a perfluorocarbon chain is described. A exhibited a surfactant behavior (cmc = 1.6 x 10(-)(5) mol/L), and the specific recognition of the galactosyl moiety grafted on A by the KbCWL1 membrane lectin was established. Preliminary experiments showed that A was able to trap free radicals in aqueous media, the shape of the observed ESR spectra being strongly dependent upon the nature of the trapped free radical.
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Acc Chem Res
August 2022
Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
Cyclometalated π-allyliridium-,-benzoate complexes discovered in the Krische laboratory display unique amphiphilic properties, catalyzing both nucleophilic carbonyl allylation and electrophilic allylation of diverse amines as well as nitronates. Given the importance of chiral amines in FDA-approved small-molecule drugs, a collaboration with medicinal chemists at Genentech that included on-site graduate student internships was undertaken to explore and expand the scope of π-allyliridium-,-benzoate-catalyzed allylic amination and related processes. As described in this Account, our collective experimental studies have unlocked asymmetric allylic aminations of exceptionally broad utility and scope.
View Article and Find Full Text PDFNanomaterials (Basel)
September 2021
Department of Chemical Engineering, i-Center for Advanced Science and Technology (iCAST), National Chung Hsing University, Taichung 40227, Taiwan.
Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and -butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1'Z)-1,1'-(1,4-phenylene) bis (--butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt) and (PtBA) star macroinitiators (MIs) can be afforded.
View Article and Find Full Text PDFACS Omega
December 2020
Institut des Biomolécules Max Mousseron, UMR 5247 CNRS-Université Montpellier-ENSCM & Avignon Université, Equipe Chimie Bioorganique et Systèmes Amphiphiles, 301 rue Baruch de Spinoza, BP 21239, Avignon 84916, Cedex 9, France.
In this work, a series of -substituted α-phenyl---butyl nitrones (PBN) were studied. Their radical-trapping properties were evaluated by electron paramagnetic resonance, with 4-CF-PBN being the fastest derivative to trap the hydroxymethyl radical (CHOH). The redox properties of the nitrones were further investigated by cyclic voltammetry, and 4-CF-PBN was the easiest to reduce and the hardest to oxidize.
View Article and Find Full Text PDFOrg Biomol Chem
July 2020
Univ. Reims Champagne-Ardenne, ICMR, CNRS UMR 7312, FR Condorcet CNRS 3417, 51687 Reims Cedex 2, France.
Condensation reactions of unprotected tetroses and pentoses with hydroxylamines afforded nitrones, which were easily converted to densely functionalized isoxazolidines in the presence of electron-poor alkenes. The 1,3-dipolar cycloaddition occurred with good facial discrimination of the chiral nitrone but under rather low endo/exo control. Stereochemistry of isomers was ascertained by chemical correlation with known derivatives from the literature.
View Article and Find Full Text PDFJ Org Chem
May 2020
Institut des Biomolécules Max Mousseron, UMR 5247 CNRS-Université Montpellier-ENSCM & Avignon Université, Equipe Chimie Bioorganique et Systèmes Amphiphiles, 301 rue Baruch de Spinoza, BP 21239, Avignon 84916 Cedex 9, France.
New derivatives of α-phenyl---butyl nitrone (PBN) bearing a hydroxyl, an acetate, or an acetamide substituent on the --butyl moiety and -substituted phenyl or naphthlyl moieties were synthesized. Their ability to trap hydroxymethyl radical was evaluated by electron paramagnetic resonance spectroscopy. The presence of two electron-withdrawing substituents on both sides of the nitronyl function improves the spin-trapping properties, with 4-HOOC-PBN-CHOAc and 4-HOOC-PBN-CHNHAc being ∼4× more reactive than PBN.
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