Sulphinic acids and esters in synthesis

Drabowicz, J.; Kiełbasiński, P.; Mikołajczyk, M.

doi:10.1002/9780470772270.ch12

Cited by 11 publications

(7 citation statements)

References 265 publications

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“…Although this result may seem unexpected, the reaction of low molecular weight SO 2 H with Michael acceptors and a-halo carbonyl compounds has been reported. 20 Conversely, sulfhydryl reactive compounds that promote mixed-disulfide formations, such as 2,2′-dipyridyl disulfide (DPS) and S-methyl methanethiosulfonate (MMTS), showed no cross-reactivity toward SO 2 H (Figures S7C and S7D). Next, we examined whether protection of free Cys residues as disulfides was sufficient to prevent cross-reactivity with NO-Ph .…”

Section: Resultsmentioning

confidence: 99%

A Chemical Approach for the Detection of Protein Sulfinylation

et al. 2015

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Protein sulfinic acids are formed by the reaction of reactive oxygen species with protein thiols. Sulfinic acid formation has long been considered an irreversible state of oxidation and is associated with high cellular oxidative stress. Increasing evidence, however, indicates that cysteine is oxidized to sulfinic acid in cells to a greater extent, and is more controlled, than first thought. The discovery of sulfiredoxin has demonstrated that cysteine sulfinic acid can be reversed, pointing to a vast array of potential implications for redox biology. Identification of the site of protein sulfinylation is crucial in clarifying the physiological and pathological effects of post-translational modifications. Currently, the only methods for detection of sulfinic acids involve mass spectroscopy and the use of specific antibodies. However, these methodologies are not suitable for proteomic studies. Herein, we report the first probe for detection of protein sulfinylation, NO-Bio, which combines a C-nitroso warhead for rapid labelling of sulfinic acid with a biotin handle. Based on this new tool, we developed a selective two-step approach. In the first, a sulfhydryl-reactive compound is introduced to selectively block free cysteine residues. Thereafter the sample is treated with NO-Bio to label sulfinic acids. This new technology represents a rapid, selective and general technology for sulfinic acid detection in biological samples. As proof of our concept, we also evaluated protein sulfinylation levels in various human lung tumour tissue lysates. Our preliminary results suggest that cancer tissues generally have higher levels of sulfinylation in comparison to matched normal tissues. A new ability to monitor protein sulfinylation directly should greatly expand the impact of sulfinic acid as a post-translational modification.

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Section: Resultsmentioning

confidence: 99%

A Chemical Approach for the Detection of Protein Sulfinylation

et al. 2015

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“…The residue was separated on a silica gel column using DCM: ethyl acetate 2:1 and, finally, with ethyl acetate as eluents for diphenyl sulfoxide 9b (88 mg, 89%) m.p. 69-71 • C; 1 A solution of (+)-(R)-4 (0.133 g, 0.5 mmol) in THF (5 mL) was treated with a solution of 2,4,6-tri-tert-butylphenylmagnesium bromide in THF (1.5 mmol) [40] at room temperature. The progress of the reaction was monitored with TLC.…”

Section: T-butyl Methyl Sulfoxide (+)-(R)-11mentioning

confidence: 99%

“…Racemic and optically active diastereoisomeric and/or enantiomeric sulfinic esters played a very important role in the development of sulfur chemistry and especially sulfur stereochemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. Preparation of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a by reacting p-toluenesulfinyl chloride 1a with (-)-(1R,3S,5R)-menthol in the presence of pyridine (Scheme 1) [16], confirmed for the first time stereogenity of a sulfinyl sulfur atom and its optical stability at room temperature [2,3].…”

Section: Introductionmentioning

confidence: 99%

“…This sulfinate was used as a precursor of the first enantiomerically pure sulfoxide, i.e., ethyl ptolyl sulfoxide [19][20][21]. Subsequently, the reaction of this diastereoisomeric sulfinates with organometallic reagents has been commonly applied to obtain a very rich family of enantiomerically pure sulfoxides and other sulfinyl derivatives as "Andersen synthesis" [1][2][3][4][5][6][7][8]. Following sulfinylation of the hydroxyl groups of a sugar moiety was used to prepare other diastereomeric sulfinates, which are used again as substrates for the synthesis of enantiomerically pure sulfinyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…The possibility of using this diastereoisomerically pure sulfite for the preparation of selected diastereoisomeric O-sulfinates results from our earlier observation that the reaction of prochiral sulfites with t-butylmagnesium chloride could be stopped on the stage of the corresponding sulfinic esters [29] and from the synthesis of enantiomerically enriched t-butanesulfinates 6 by the reaction of prochiral This sulfinate was used as a precursor of the first enantiomerically pure sulfoxide, i.e., ethyl p-tolyl sulfoxide [19][20][21]. Subsequently, the reaction of this diastereoisomeric sulfinates with organometallic reagents has been commonly applied to obtain a very rich family of enantiomerically pure sulfoxides and other sulfinyl derivatives as "Andersen synthesis" [1][2][3][4][5][6][7][8]. Following sulfinylation of the hydroxyl groups of a sugar moiety was used to prepare other diastereomeric sulfinates, which are used again as substrates for the synthesis of enantiomerically pure sulfinyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity

et al. 2020

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The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P212121, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.

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C−C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates

Schenk

Bezler

1998

Eur. J. Inorg. Chem.

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Sulphinic acids and esters in synthesis

Cited by 11 publications

References 265 publications

A Chemical Approach for the Detection of Protein Sulfinylation

A Chemical Approach for the Detection of Protein Sulfinylation

Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity

C−C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates

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