Optically active trivalent phosphorus compounds. 2. Reactivity of alkylthio- and alkylselenophosphonium salts. The first stereospecific synthesis of a chiral phosphinite

Omelańczuk, Jan; Mikołajczyk, M.

doi:10.1021/ja00518a026

Cited by 59 publications

(30 citation statements)

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“…Literature values for S-alkylphosphonium ion 31 P NMR shifts are roughly 40–50 ppm, consistent with the observed resonances for 5 and 6 (32–34). These SP + ions also represent known intermediates in phosphine-mediated disulfide reductions.…”

Section: Resultssupporting

confidence: 84%

Water-Soluble Triarylphosphines as Biomarkers for Protein S-Nitrosation

Bechtold

Reisz

Klomsiri³

et al. 2010

ACS Chem. Biol.

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S-Nitrosothiols (RSNOs) represent an important class of post-translational modifications that preserve and amplify the actions of nitric oxide and regulate enzyme activity. Several regulatory proteins are now verified targets of cellular S-nitrosation and the direct detection of S-nitrosated residues in proteins has become essential to better understand RSNO-mediated signaling. Current RSNO detection depends on indirect assays that limit their overall specificity and reliability. Herein, we report the reaction of S-nitrosated cysteine, glutathione, and a mutated C165S alkyl hydroperoxide reductase with the water-soluble phosphine, tris(4,6-dimethyl-3-sulfonatophenyl)phosphine trisodium salt hydrate (TXPTS). A combination of NMR and MS techniques reveals these reactions produce covalent S-alkylphosphonium ion adducts (with S-P + connectivity), TXPTS oxide and a TXPTS-derived aza-ylide. Mechanistically, this reaction may proceed through an S-substituted azaylide or the direct displacement of nitroxyl from the RSNO group. This work provides a new means for detecting and quantifying S-nitrosated species in solution and suggests that phosphines may be useful tools for understanding the complex physiological roles of S-nitrosation and its implications in cell signaling and homeostasis. KeywordsS-nitrosothiol; triarylphosphine; aza-ylide; S-alkylphosphonium ion; protein labeling; chemical ligation; nitrosative stress Reactive oxygen and nitrogen species (ROS/RNS) affect cellular signaling processes at concentrations far below those required to inflict oxidative damage (1-4). The over-oxidation and metabolism of nitric oxide (NO), an endogenous cell signaling agent, produces several RNS including nitrogen dioxide and nitrite, which can generate competent nitrosation agents (5,6). Nitrosation of cysteine sites yields S-nitrosothiols (RSNOs) that preserve, modulate, and amplify the actions of NO. This selective and reversible process represents an important postCorrespondence to: S. Bruce King, kingsb@wfu.edu. † Department of Chemistry ‡ Center for Structural Biology § Department of Molecular Medicine Supporting Information available: Experimental details for the synthesis of Cys-SNO, GSNO and AhpC-SNO. 31 P and 13 C NMR spectra, UV/vis data and LC-MS results for various reactions. ESI-TOF-MS controls and x-ray structural data for 1. This material is available free of charge via the Internet at http://pubs.acs.org. (3,(6)(7)(8). Several proteins have been identified as targets of cellular S-nitrosation including glyceraldehyde-3-phosphate dehydrogenase (GAPDH), papain, hemoglobin (Hb), and several caspases (5,9-12). Inflammatory stimuli, including RNS, increase overall cellular RSNO formation, which further mediates the inflammatory process (9,(13)(14)(15)(16)(17). Direct detection and specific identification of S-nitrosated residues in proteins is essential to better understand RSNO-mediated signaling. Current techniques, such as the biotin switch assay, Saville assay, and chemiluminescencebased methods, are ind...

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Section: Resultssupporting

confidence: 84%

Water-Soluble Triarylphosphines as Biomarkers for Protein S-Nitrosation

Bechtold

Reisz

Klomsiri³

et al. 2010

ACS Chem. Biol.

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“…Therefore we considered how we could generate a pseudophosphonium salt 25 with a non-nucleophilic counter-ion, in order to stop any racemisation process. This caused us to re-consider alkylation of the PO bond, 23 in particular the work of Imamoto and coworkers.…”

mentioning

confidence: 99%

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

2012

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“…Using our standard conditions, the reaction proceeded smoothly, but purification of the product proved to be cumbersome as the reaction byproduct triphenylphosphane sulfide cannot be easily removed by column chromatography. Experiments to remove the sulfide by different filtration techniques were unsuccessful, other methods like alkylation with methyl trifluoromethanesulfonate [24] could not be utilized because of possible alkylation of product 8. So we examined the transformation of triphenylphosphane sulfide to the corresponding oxide by trifluoroacetic anhydride as described by Michalski.…”

Section: Synthesis Of Carbamate 8 and Development Of An Advanced Purimentioning

confidence: 99%

A Formal Total Synthesis of Virantmycin: A Modular Approach towards Tetrahydroquinoline Natural Products

2006

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A synthesis of an advanced intermediate towards the racemic form of the antiviral agent virantmycin has been developed featuring an intramolecular aza‐xylylene Diels–Alder reaction. The required arylthiocarbamate has been constructed using an efficient oxidative cyclization strategy. A novel synthetic approach to chlorine‐substituted allylic alcohols using an unprecedented palladium‐catalyzed cross‐coupling reaction of α,β‐unsaturated ketones and protected propargylic alcohols is reported.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Optically active trivalent phosphorus compounds. 2. Reactivity of alkylthio- and alkylselenophosphonium salts. The first stereospecific synthesis of a chiral phosphinite

Cited by 59 publications

References 3 publications

Water-Soluble Triarylphosphines as Biomarkers for Protein S-Nitrosation

Water-Soluble Triarylphosphines as Biomarkers for Protein S-Nitrosation

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

A Formal Total Synthesis of Virantmycin: A Modular Approach towards Tetrahydroquinoline Natural Products

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