- An improved process for preparation of S-Acetyl-l-glutathione
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An efficient one-step synthesis of S-acetyl-l-glutathione has been developed in a DMF-TFA mixed solvent with CoCl2 as catalyst. This process not only has the advantages of selective acylation of the glutathione thiol group without involving the free amino but also highlights recycling of the relatively costly solvent TFA, which improves the yield to 91% and quality to 99.7%. The reaction is cost-effective, efficient, and easy to scale-up.
- Fu, Kai,Wang, Qiu-Fen,Zhan, Fu-Xu,Yang, Liu,Yang, Qian,Zheng, Geng-Xiu
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- Live-Cell Protein Modification by Boronate-Assisted Hydroxamic Acid Catalysis
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Selective methods for introducing protein post-translational modifications (PTMs) within living cells have proven valuable for interrogating their biological function. In contrast to enzymatic methods, abiotic catalysis should offer access to diverse and new-to-nature PTMs. Herein, we report the boronate-assisted hydroxamic acid (BAHA) catalyst system, which comprises a protein ligand, a hydroxamic acid Lewis base, and a diol moiety. In concert with a boronic acid-bearing acyl donor, our catalyst leverages a local molarity effect to promote acyl transfer to a target lysine residue. Our catalyst system employs micromolar reagent concentrations and affords minimal off-target protein reactivity. Critically, BAHA is resistant to glutathione, a metabolite which has hampered many efforts toward abiotic chemistry within living cells. To showcase this methodology, we installed a variety of acyl groups inE. colidihydrofolate reductase expressed within human cells. Our results further establish the well-known boronic acid-diol complexation as abona fidebio-orthogonal reaction with applications in chemical biology and in-cell catalysis.
- Adamson, Christopher,Kajino, Hidetoshi,Kanai, Motomu,Kawashima, Shigehiro A.,Yamatsugu, Kenzo
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supporting information
p. 14976 - 14980
(2021/09/29)
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- Ethynylation of Cysteine Residues: From Peptides to Proteins in Vitro and in Living Cells
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Current approaches to introduce terminal alkynes for bioorthogonal reactions into biomolecules still present limitations in terms of either reactivity, selectivity, or adduct stability. We present a method for the ethynylation of cysteine residues based on the use of ethynylbenziodoxolone (EBX) reagents. The acetylene group is directly introduced onto the thiol group of cysteine and can be used for copper-catalyzed alkyne-azide cycloaddition (CuAAC) without further processing. Labeling proceeded with reaction rates comparable to or higher than the most often used iodoacetamide on peptides or maleimide on the antibody trastuzumab, and high cysteine selectivity was observed. The reagents were also used in living cells for cysteine proteomic profiling and displayed improved coverage of the cysteinome compared to previously reported iodoacetamide or hypervalent iodine reagents. Fine-tuning of the EBX reagents allows optimization of their reactivity and physical properties.
- Tessier, Romain,Nandi, Raj Kumar,Dwyer, Brendan G.,Abegg, Daniel,Sornay, Charlotte,Ceballos, Javier,Erb, Stéphane,Cianférani, Sarah,Wagner, Alain,Chaubet, Guilhem,Adibekian, Alexander,Waser, Jerome
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supporting information
p. 10961 - 10970
(2020/05/18)
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- Direct Observation of Acyl Nitroso Compounds in Aqueous Solution and the Kinetics of Their Reactions with Amines, Thiols, and Hydroxamic Acids
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Acyl nitroso compounds or nitrosocarhonyls (RC(O)N=O) are reactive short-lived electrophiles, and their hydrolysis and reactions with nucleophiles produce HNO. Previously, direct detection of acyl nitroso species in nonaqueous media has been provided by time-resolved infrared spectroscopy demonstrating that its half-life is about 1 ms. In the present study hydroxamic acids (RC(O)NHOH) are oxidized electrochemically in buffered aqueous solutions (pH 5.9-10.2) yielding transient species characterized by their maximal absorption at 314-330 nm. These transient species decompose via a first-order reaction yielding mainly HNO and the respective carboxylic acid and therefore are ascribed to RC(O)N=O. The sufficiently long half-life of RC(O)N=O in aqueous solution allows for the first time the study of the kinetics of its reactions with various nucleophiles demonstrating that the nucleophilic reactivity follows the order thiolate > hydroxamate > amine. Metal chelates of CH3C(O)NHOH catalyze the hydrolysis of CH3C(O)N=O at the efficacy order of CuII > ZnII > NiII > CoII where only CuII catalyzes the hydrolysis also in the absence of the hydroxamate. Finally, oxidation of hydroxamic acids generates HNO, and the rate of this process is determined by the half-life of the respective acyl nitroso compound.
- Maimon, Eric,Lerner, Ana,Samuni, Amram,Goldstein, Sara
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p. 7006 - 7013
(2018/09/06)
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- MOLECULARLY IMPRINTED POLYMERS FOR THE RECOGNITION OF GLUTATHIONE GSH, METHODS FOR PREPARING SAME AND USES THEREOF
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The present invention relates to new molecularly imprinted polymers which are suitable for the selective recognition of glutathione GSH and/or of an analog thereof, and in particular which are of use for the treatment of media comprising in particular a mixture of glutathione GSH, and/or of an analog thereof, with GSH adducts.
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- Process for the preparation of glutathione S-acyl derivatives, compounds obtained from said process and an intermediate useful for the preparation thereof
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A selective and high yield process for S-acylating glutathione, comprising the eaction between glutathione and an acyl chloride or a carboxylic anhydride in trifluoroacetic acid is described.
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