The One-Pot Synthesis and Diels-Alder Reactivity of 2,5-Dihydrothiophene- 1,1-dioxide-3-carboxylic Acid

Andrade, Genara S.; Berkner, Joachim E.; Liotta, Charles L.; Eckert, Charles A.; Schiraldi, David A.; Collard, David M.

doi:10.1081/scc-120024845

Cited by 9 publications

(6 citation statements)

References 12 publications

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“…[43][44][45] This cheletropic reaction is known to be reversible under elevated temperature. 43,46,47 Thus, we hypothesized that incorporation of 1,3-butadiene into a highly porous structure may improve the removal of sulfur dioxide. Furthermore, the material may be regenerated for additional uses.…”

Section: R a F Tmentioning

confidence: 99%

Investigating the cheletropic reaction between sulfur dioxide and butadiene-containing linkers in UiO-66

2018

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UiO-66 and a muconic acid functionalized derivative of UiO-66 (UiO-66-MA) were synthesized via the solvothermal method to determine if the muconic acid could undergo a cheletropic reaction in the presence of sulfur dioxide inside the metal-organic framework (MOF). Both MOFs were exposed to a constant flow of sulfur dioxide, and UiO-66-MA was observed to take up three times more sulfur dioxide than unfunctionalized UiO-66. Despite the improved uptake of sulfur dioxide in UiO-66-MA, NMR and IR data indicate that no chemical change occurred to the muconic acid indicating that a cheletropic reaction did not occur. We thus propose that the increased adsorption is due to either an interaction between the sulfur dioxide and unbound carboxylic acid from the muconic acid or a favourable interaction between the butadiene of muconic acid and sulfur dioxide.

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Section: R a F Tmentioning

confidence: 99%

Investigating the cheletropic reaction between sulfur dioxide and butadiene-containing linkers in UiO-66

2018

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“…route to 3-carboxy-3-sulfolene was found by Collard and co-workers, who synthesized 3-sulfolene-3-carboxylic acid (54) in one step from 3-sulfolene and carbon dioxide (in the presence of DBU) in a 45% yield. 36 Reaction of 54 with maleic anhydride and other electron-deficient olefins led to the expected Diels-Alder adducts in excellent yields. 36 Scheme 12 Access to 3-carboxy-3-sulfolenes 3-Cyano-3-sulfolene (56) was produced through a thia-Michael/Dieckmann reaction between acrylonitrile and methyl thioglycolate to afford 55.…”

Section: Syn Thesismentioning

confidence: 99%

“…36 Reaction of 54 with maleic anhydride and other electron-deficient olefins led to the expected Diels-Alder adducts in excellent yields. 36 Scheme 12 Access to 3-carboxy-3-sulfolenes 3-Cyano-3-sulfolene (56) was produced through a thia-Michael/Dieckmann reaction between acrylonitrile and methyl thioglycolate to afford 55. A three-step reduction/mesylation/ elimination/oxidation sequence provided 56 in good yield (Scheme 13).…”

Section: Syn Thesismentioning

confidence: 99%

3-Sulfolenes and Their Derivatives: Synthesis and Applications

Brant

Wulff

2015

Synthesis

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The diverse substitution patterns available to 3-sulfolenes have long made them useful for the preparation of multi-substituted 1,3-diene equivalents. More recently, the 3-sulfolene motif itself (or its reduced sulfolane congener) is finding increasing application as a structural element in the creation of molecules for biological applications. This review describes various methods to afford 3-sulfolene building blocks and their derivatives. Selected applications in synthetic and medicinal chemistry are also discussed. 1 Introduction 2 The Preparation of Monocyclic Sulfolene Building Blocks 2.1 Sulfolenes through Electrophilic Addition 2.1.1 Sulfolenes through Nucleophilic Addition to 4-Bromo-2-sulfolene 2.2 Sulfolenes through Oxidation of a Thiol Precursor 2.3 Sulfolenes through Noble Metal Catalysis 2.4 Sulfolenes through Deprotonation Followed by Alkylation 3 Synthesis of Bicyclic Sulfolenes and Their Derivatives 3.

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“…

With the aim of further extending our knowledge about the reactivity of 3-thiolene 1,1-dioxide with respect to PH-acids and also in order to obtain new representatives of phosphorus-containing tetrahydrothiophenes, we have studied for the first time the reaction of thiolene 1 with secondary phosphine sulfides, using as an example bis(2-phenylethyl)phosphine sulfide (2) which can be readily obtained from the accessible bis(2-phenylethyl)phosphine [[8] and sulfur.

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mentioning

confidence: 99%

“…Functionalized derivatives of 3-thiolene 1,1-dioxide (1) continue to attract attention as building blocks for organic synthesis, intermediates for obtaining biologically active substances, complexing solvents, and models for studying substituent effects in dihydrothiophenes [1][2][3][4].…”

mentioning

confidence: 99%

First example of hydro-thiophosphorylation of 3-thiolene 1,1-dioxide

Гусарова

Иванова

Bogdanova

et al. 2004

Chem Heterocycl Compd

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Keywords: bis(2-phenylethyl)phosphine sulfide, 3-[di(2-phenylethyl)thiophosphoryl]tetrahydro-1H-thiophene-1,1-dione, 3-thiolene 1,1-dioxide, nucleophilic addition.Functionalized derivatives of 3-thiolene 1,1-dioxide (1) continue to attract attention as building blocks for organic synthesis, intermediates for obtaining biologically active substances, complexing solvents, and models for studying substituent effects in dihydrothiophenes [1][2][3][4].Synthesis of phosphorus-containing sulfolanes based on thiolene 1 opens up new prospects for constructing functionalized extraction and complexing agents as well as special solvents and ligands for metal complex catalysts. Information about reactions of thiolene 1 with PH acids includes data on nucleophilic and radical addition of dialkylphosphites [5,6], and also addition of primary and secondary phosphines and phosphine oxides [7].With the aim of further extending our knowledge about the reactivity of 3-thiolene 1,1-dioxide with respect to PH-acids and also in order to obtain new representatives of phosphorus-containing tetrahydrothiophenes, we have studied for the first time the reaction of thiolene 1 with secondary phosphine sulfides, using as an example bis(2-phenylethyl)phosphine sulfide (2) which can be readily obtained from the accessible bis(2-phenylethyl)phosphine [[8] and sulfur. Since phosphine sulfides are ambident compounds [9] and prototropism is possible in thiolene 1, the direction and outcome of the reaction under study were not predictable.We found that under mild conditions (45-50°C, 1 h, KOH, DMSO), phosphine sulfide 2 can add to thiolene 1 chemospecifically and regiospecifically, forming 3-[di(2-phenylethyl)thiophosphoryl]tetrahydro-1H-thiophene-1,1-dione (3) in 72% yield. We did not observe the SH tautomer of phosphine sulfide 2a in the reaction mixture among the products of hydrothiophosphorylation of thiolene 1. Without KOH and also under radical initiation conditions (65°C, 6 h, AIBN [azoisobutyronitrile]) and with all other conditions the same, hydrothiophosphorylation of thiolene 1 does not occur. This is support for the nucleophilic nature of this reaction, probably occurring through the electrophilic isomer 1a formed as a result of a prototropic shift of the double bond in the dihydrothiophene ring [7]. __________________________________________________________________________________________

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The One-Pot Synthesis and Diels-Alder Reactivity of 2,5-Dihydrothiophene- 1,1-dioxide-3-carboxylic Acid

Cited by 9 publications

References 12 publications

Investigating the cheletropic reaction between sulfur dioxide and butadiene-containing linkers in UiO-66

Investigating the cheletropic reaction between sulfur dioxide and butadiene-containing linkers in UiO-66

3-Sulfolenes and Their Derivatives: Synthesis and Applications

First example of hydro-thiophosphorylation of 3-thiolene 1,1-dioxide

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