Regio‐ and Stereocontrolled Synthesis of (<i>Z</i>)‐α‐(Phenylseleno)sulfinyl and ‐sulfonyl Alkenes via Sulfenic Acids, and a Study of their Reactivity

Aversa, M. C.; Barattucci, Anna; Bonaccorsi, Paola; Temperini, Andrea

doi:10.1002/ejoc.201100759

Cited by 19 publications

(7 citation statements)

References 29 publications

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“…Further increasing the reaction temperature raised the yield of 3 aa to 73 % (Table 1, entry 4). A literature survey revealed that a brief study was carried out on thermolysis of β‐sulfinyl ester to emphasize the influence of carboxylate group in the sulfenic acid formation via trapping the sulfenic acid with selected alkynes [10d–h,12] . However, to the best of our knowledge, the comprehensive study exploring the synthetic utility of various β‐sulfinyl esters with a wide range of alkynes and detailed mechanistic studies has not been realized yet.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

et al. 2021

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Methods to synthesize α‐substituted alkenyl sulfoxides are highly useful as they are widely used to construct diverse molecules of high synthetic importance. We have described a synthetic route for expedient access to the numerous α‐substituted alkenyl sulfoxides from alkynes and β‐sulfinyl esters. This protocol exhibits a vast substrate scope, readily accommodates a wide range of functional groups, and is scalable in a gram‐scale. Besides, we demonstrated a direct synthesis of alkenyl sulfoxides from thiols via the in situ generation of the requisite β‐sulfinyl ester. The ensuing α‐substituted alkenyl sulfoxide product was readily transformed into benzofuran and sulfonyl derivatives. Mechanistic investigations were done to comprehend the reaction mechanism.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

et al. 2021

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“…The nucleophilicity of organic sulfenic acids has been utilized in synthetically useful routes toward sulfones, sulfoxides and alkenes, and forms the basis for their reaction chemistry with 7-chloro-4-nitrobenzo-2oxa-1,3-diazole for spectroscopic protein -SOH detection [15][16][17][18]. Lone electron pairs on the -SOH oxygen provide a-effect sulfur nucleophilicity, and the potential for oxygen nucleophilicity has also been documented [19,20].…”

Section: Introductionmentioning

confidence: 99%

Thiol‐blocking electrophiles interfere with labeling and detection of protein sulfenic acids

et al. 2013

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Cellular exposure to reactive oxygen species induces the rapid oxidation of DNA, proteins, lipids, and other biomolecules. At the proteome level, cysteine thiol oxidation is a prominent post-translational process implicated in normal physiology and numerous pathologies. Methods for investigating protein oxidation include direct labeling with selective chemical probes and indirect tag-switch techniques. Common to both approaches is a chemical blocking of free thiols with reactive electrophiles to prevent post-lysis oxidation or other thiol-mediated cross-reactions. These reagents are used in large excess and their reactivity with cysteine sulfenic acid, a critical oxoform in numerous proteins, has not been investigated. Here we report the reactivity of three thiol-blocking electrophiles, iodoacetamide, N-ethylmaleimide, and methyl methanethiosulfonate, with protein sulfenic acid and dimedone, the structural core of many sulfenic acid probes. We demonstrate that covalent cysteine -SOR (product) species are susceptible to reduction by DTT, TCEP, and ascorbate, regenerating protein thiols, or in the case of ascorbate, more highly oxidized species. The implications of this reactivity on detection methods for protein sulfenic acids and S-nitrosothiols are discussed.

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“…Synthetic Procedures: The starting sulfoxides 3,3′,3″‐[(2,4,6‐triethyl‐1,3,5‐benzenetriyl)tris(methylenesulfinyl)]trispropanoic acid 1,1′,1″‐trimethyl ester 4 10a,10c and 3‐(phenylsulfinyl)propanoic acid methyl ester 7 10b were synthesized following already published methods.…”

Section: Methodsmentioning

confidence: 99%

Mono‐ and Trinuclear Tripodal Platinum(II) Chelated Complexes Containing a Pyridine/Sulfoxide Based Anchoring Framework

et al. 2013

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New tripodal ligands 2,4,6-triethyl-1,3,5-tris{[1-(2-pyridinyl)ethenyl]sulfinylmethyl}benzenes 6, characterized by three pendant chains each containing both sulfoxide and pyridine moieties, were synthesized from the corresponding sulfenic acid and 2-ethynylpyridine. Two diastereomeric mixtures were obtained and separated, one racemic mixture 6a, having a C 3 symmetry axis and the other 6b with no symmetry. With the aim of studying the coordination ability of these chelating-κN,κS type ligands, monobranched racemic [1-(2pyridinyl)ethenyl]sulfinylbenzene 9 was also synthesized. Upon addition of an equivalent amount of the monochelating ligand 9 or the tripodal species 6a to a CD 3 CN solution of a platinum(II) complex of the type cis-[PtMe 2 (Me 2 SO) 2 ] (Pt1) or [a]

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Regio‐ and Stereocontrolled Synthesis of (Z)‐α‐(Phenylseleno)sulfinyl and ‐sulfonyl Alkenes via Sulfenic Acids, and a Study of their Reactivity

Cited by 19 publications

References 29 publications

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

Thiol‐blocking electrophiles interfere with labeling and detection of protein sulfenic acids

Mono‐ and Trinuclear Tripodal Platinum(II) Chelated Complexes Containing a Pyridine/Sulfoxide Based Anchoring Framework

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