Cesium (<i>Z</i>)‐2‐Carbomethoxyethenethiolate: A Reagent for the Preparation of (<i>Z</i>)‐2‐Carbomethoxyethenyl Thioethers Including Selected Cysteine and Homocysteine Derivatives

O’Donnell, Jennifer S.; Singh, Sunita; Metcalf, Thomas A.; Schwan, Adrian L.

doi:10.1002/ejoc.200801025

Cited by 10 publications

(9 citation statements)

References 39 publications

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“…The deprotection of a thioacetic acid-propiolate Michael adduct with CsCO 3 has also been used as an efficient route to vinylic thioethers including cysteine and homocysteine derivatives (Scheme 10). 129 It is interesting to note that subsequent intermolecular reactions were not reported despite the nucleophilicity of the thiolate species. The thiol-yne reaction was also not quantitative (yield = 79%) in this example despite the low pKa of the thiol, but this can be rationalized by the fact that it is a secondary thiol and imidazole is a relatively poor base.…”

Section: Bioconjugationmentioning

confidence: 99%

Click Nucleophilic Conjugate Additions to Activated Alkynes: Exploring Thiol-yne, Amino-yne, and Hydroxyl-yne Reactions from (Bio)Organic to Polymer Chemistry

et al. 2021

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The 1,4-conjugate addition reaction between activated alkynes or acetylenic Michael acceptors and nucleophiles (i.e., the nucleophilic Michael reaction) is a historically useful organic transformation. Despite its general utility, the efficiency and outcomes can vary widely and are often closely dependent upon specific reaction conditions. Nevertheless, with improvements in reaction design, including catalyst development and an expansion of the substrate scope to feature more electrophilic alkynes, many examples now present with features that are congruent with Click chemistry. Although several nucleophilic species can participate in these conjugate additions, ubiquitous nucleophiles such as thiols, amines, and alcohols are commonly employed and, consequently, among the most well developed. For many years, these conjugate additions were largely relegated to organic chemistry, but in the last few decades their use has expanded into other spheres such as bioorganic chemistry and polymer chemistry. Within these fields, they have been particularly useful for bioconjugation reactions and step-growth polymerizations, respectively, due to their excellent efficiency, orthogonality, and ambient reactivity. The reaction is expected to feature in increasingly divergent application settings as it continues to emerge as a Click reaction.

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Section: Bioconjugationmentioning

confidence: 99%

Click Nucleophilic Conjugate Additions to Activated Alkynes: Exploring Thiol-yne, Amino-yne, and Hydroxyl-yne Reactions from (Bio)Organic to Polymer Chemistry

et al. 2021

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“…Barua and coworkers [16] have already demonstrated that arenesulfenyl chlorides add across the triple bond of 3‐ p ‐bromophenyl‐2‐propynol in yields >55 %. Comparable trials with 1 c , the sulfenyl chloride possibly accessible from ( Z )‐2‐carbomethoxyethenyl thiolacetate [17] did not produce sulfinyl allene. Clearly the common protocols for making sulfenate esters and hence alkyl allenyl sulfoxides are not suitable for the planned chemistry.…”

Section: Resultsmentioning

confidence: 88%

N‐Sulfanylimides as the Sulfur Source for Alkyl Allenyl Sulfoxides via [2,3]‐Sigmatropic Rearrangement

et al. 2021

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Sulfenyl chlorides are a reliable starting material to access allenyl sulfoxides with aryl or haloalkyl groups by way of sulfenate ester formation followed by [2,3]-sigmatropic rearrangement. Application of the chemistry of alkanesulfenyl chlorides is much less common due to competing fates along the reaction pathway. In this paper, N-sulfanylsuccimides (thiosuccinimides) are shown to be a viable replacement for sulfenyl chlorides. A number of allenyl alkyl sulfoxides are prepared in fair to good yields (21-73 %, 21 examples). In addition, some butyn-1,4-diols can be selectively monofunctionalized to form allenyl sulfoxides (26-71 %) with a hydroxyalkyl group geminal to the sulfur. Butynediols also permit synthetic access to dienes via successive sulfenate ester formation and [2,3]-sigmatropic rearrangement reactions. N-2-Trimethylsilylethylthosucinimides were among the highest yielding of the thioimides.

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“…Z,E-and Z,Z-bis [2-carbomethoxyethenyl] sulfoxides (2j) and homocysteine derivative 2l were prepared using the newly introduced caesium 2-Z-carbomethoxyethenethiolate methodology. 21 Other methods may be suitable for the preparation of the requisite sulfoxides 2, such as the sulfenic addition protocol of Aversa et al, 22 which would yield selectively the E-isomer, but this was not exploited for the current work.…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic attack of 2-sulfinyl acrylates: A mild and general approach to sulfenic acid anions

2010

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An increasing number of reactions of sulfenic acid anions are being demonstrated in the literature. As such, mild, general and reliable means for the generation of sulfenates are due. In the current paper, an addition/elimination of 2-sulfinyl acrylates using various nucleophiles is demonstrated and evaluated as a protocol for alkane- and arenesulfenate generation. Cyclohexanethiolate, methoxide and n-butyllithum each exhibit some merit for the reaction, and the thiolate is established as a mild, selective and effective reagent to release sulfenates from 2-sulfinyl acrylates. The stereospecificity of the addition/elimination of each nucleophile is recognized, and an explanation for the specificity is offered for thiolate and methoxide.

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Cesium (Z)‐2‐Carbomethoxyethenethiolate: A Reagent for the Preparation of (Z)‐2‐Carbomethoxyethenyl Thioethers Including Selected Cysteine and Homocysteine Derivatives

Cited by 10 publications

References 39 publications

Click Nucleophilic Conjugate Additions to Activated Alkynes: Exploring Thiol-yne, Amino-yne, and Hydroxyl-yne Reactions from (Bio)Organic to Polymer Chemistry

Click Nucleophilic Conjugate Additions to Activated Alkynes: Exploring Thiol-yne, Amino-yne, and Hydroxyl-yne Reactions from (Bio)Organic to Polymer Chemistry

N‐Sulfanylimides as the Sulfur Source for Alkyl Allenyl Sulfoxides via [2,3]‐Sigmatropic Rearrangement

Nucleophilic attack of 2-sulfinyl acrylates: A mild and general approach to sulfenic acid anions

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