PEG-400 as a recyclable solvent in the synthesis of β-arylthio-α,β-unsaturated esters, ketone and aldehyde under base and catalyst-free conditions

Borges, Elton de Lima; Nobre, Patrick C.; Silva, Márcio Santos da; Jacob, Raquel G.; Lenardão, Eder J.; Perin, Gelson

doi:10.1016/j.jece.2016.03.027

Cited by 9 publications

(7 citation statements)

References 35 publications

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“…Moreover, the pH of the aqueous reaction solvent can have a pronounced effect on the reaction rate and overall conversion (Table 3). 67 "Greener" recyclable solvents such as polyethylene glycol (PEG) 77 have also shown promise for the thiol-yne Michael addition. For this uncatalyzed addition of thiophenol to ethyl 3-phenylpropiolate, yields near 90% were achieved at 60 °C, which falls short of the Click definition but could still be greatly improved by simply employing organobase catalysts.…”

Section: Trends In Reactivitymentioning

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: Trends In Reactivitymentioning

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 most common reaction involves thiolates generated in situ by adding a base to a solution of a thiol and ynones, 46−48,414−416 but some reactions have also been carried out under neutral conditions. 32,349,417 A few alkanethiols 415 and dithiols 45−48,349,414−416 have been applied, but also some thiophenols. 32,244,417 Furthermore, most reactions have been carried out at room temperature or below, [45][46][47]414,416 but heating as high as 80 °C has also been reported.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…32,349,417 A few alkanethiols 415 and dithiols 45−48,349,414−416 have been applied, but also some thiophenols. 32,244,417 Furthermore, most reactions have been carried out at room temperature or below, [45][46][47]414,416 but heating as high as 80 °C has also been reported. 244,417 The products obtained from conjugate addition of thiols to ynones depend on the number of thiol groups available per ynone moiety.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…32,244,417 Furthermore, most reactions have been carried out at room temperature or below, [45][46][47]414,416 but heating as high as 80 °C has also been reported. 244,417 The products obtained from conjugate addition of thiols to ynones depend on the number of thiol groups available per ynone moiety. When the ratio is close to 1:1, vinyl sulfides are generally formed in good to excellent yields as mixtures of isomers with an E/Z ratio that varies quite a lot, 32,34,417 but when increased to 2:1 ratio, thioacetals are usually furnished in excellent yields.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…244,417 The products obtained from conjugate addition of thiols to ynones depend on the number of thiol groups available per ynone moiety. When the ratio is close to 1:1, vinyl sulfides are generally formed in good to excellent yields as mixtures of isomers with an E/Z ratio that varies quite a lot, 32,34,417 but when increased to 2:1 ratio, thioacetals are usually furnished in excellent yields. 415 Ynones 26, 71, and 350 have been chosen to illustrate the synthesis of products 498−501 (Scheme 218).…”

Section: Conjugate Additionsmentioning

confidence: 99%

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Conjugated Ynones in Organic Synthesis

2019

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This review article will consider the preparation and application of ynones in synthetic organic chemistry. Concerning the preparation of these bifunctional compounds, several methodologies starting from propargyl alcohols, acyl derivatives, both by using alkynylmetal reagents or by transition metal (mainly palladium and copper) catalyzed alkynylations, carbon monoxide (carbonylation of terminal alkynes and alkenes), and other substrates will be discussed. The reactivity and synthetic applications of ynones will be focused on conjugate additions with boron-, carbon-, nitrogen-, oxygen-, and other heteroatom-containing nucleophiles, as well as radicals. Then, cycloaddition processes will include [2 + 2] cycloadditions, [3 + 2] 1,3-dipolar cycloadditions (with azides, nitrones, azomethine imines and ylides, nitrile oxides, diazo compounds, and other dipoles), and [4 + 2] cycloadditions (mainly Diels–Alder-type reactions). The reduction of the triple bond, addition to the carbonyl group (using carbon- and heteronucleophiles and reductions), and other not so commonly used processes (such as aldol reactions, cyclizations, and isomerizations) will be considered at the end.

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Thiol‐Specific Silicon‐Containing Conjugating Reagent: β‐Silyl Alkynyl Carbonyl Compounds

Teng,

Zhang,

et al. 2023

Angewandte Chemie

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Site‐specific modification of thiol‐containing biomolecules has been recognized as a versatile and powerful strategy for probing our biological systems and discovering novel therapeutics. The addition of lipophilic silicon moiety opens up new avenues for multi‐disciplinary research with broad applications in both the medicinal and material sciences. However, adhering to the strict biocompatibility requirements, and achieving the introduction of labile silicon handle and high chemo‐selectivity have been formidable. In this paper, we report silicon‐based conjugating reagents including β‐trialkylsilyl and silyl ether‐tethered alkynones that selectively react with thiols under physiological conditions. The pH‐neutral, metal‐free and additive‐free reaction yields stable products with broad substrate compatibility and full retention of silicon handles in most cases. Besides simple aliphatic and aromatic thiols, this approach is applicable in the labeling of thiols present in proteins, sugars and payloads, thereby expanding the toolbox of thiol conjugation.

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PEG-400 as a recyclable solvent in the synthesis of β-arylthio-α,β-unsaturated esters, ketone and aldehyde under base and catalyst-free conditions

Cited by 9 publications

References 35 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

Conjugated Ynones in Organic Synthesis

Thiol‐Specific Silicon‐Containing Conjugating Reagent: β‐Silyl Alkynyl Carbonyl Compounds

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