Recent Advances in the Synthesis of Thiophene Derivatives by Cyclization of Functionalized Alkynes

Mancuso, Raffaella; Gabriele, Bartolo

doi:10.3390/molecules191015687

Cited by 80 publications

(24 citation statements)

References 106 publications

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“…After the oxidation of the Fe(II) sulfonium species ( 11 ) to its Fe(III) form ( 12 ), the modulation of the acidity of the β protons by the sulfonium favors a base-induced deprotonation of the group bonded to the sulfur atom, thus promoting the generation of the Fe(III) sulfheme species ( 13 ) along with vinylglycine via an elimination reaction. This scenario parallels the involvement of sulfonium species as intermediates during the synthesis of thiophene derivatives by the cyclization of functionalized alkynes51, during the conversion of Cys or GSH into their respective α,β-unsaturated dehydroalanyl derivatives525354 or during the reactivity of dibromobimane with RSH to produce a bimane thioether55.…”

Section: Resultsmentioning

confidence: 82%

Sulfheme formation during homocysteine S-oxygenation by catalase in cancers and neurodegenerative diseases

et al. 2016

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Accumulating evidence suggests that abnormal levels of homocysteine are associated with vascular dysfunctions, cancer cell proliferation and various neurodegenerative diseases. With respect to the latter, a perturbation of transition metal homeostasis and an inhibition of catalase bioactivity have been reported. Herein, we report on some of the molecular bases for the cellular toxicity of homocysteine and demonstrate that it induces the formation of sulfcatalase, an irreversible inactive state of the enzyme, without the intervention of hydrogen sulfide. Initially, homocysteine reacts with native catalase and/or redox-active transition metal ions to generate thiyl radicals that mediate compound II formation, a temporarily inactive state of the enzyme. Then, the ferryl centre of compound II intervenes into the unprecedented S-oxygenation of homocysteine to engender the corresponding sulfenic acid species that further participates into the prosthetic heme modification through the formation of an unusual Fe(II) sulfonium. In addition, our ex cellulo studies performed on cancer cells, models of neurodegenerative diseases and ulcerative colitis suggest the likelihood of this scenario in a subset of cancer cells, as well as in a cellular model of Parkinson's disease. Our findings expand the repertoire of heme modifications promoted by biological compounds and point out another deleterious trait of disturbed homocysteine levels that could participate in the aetiology of these diseases.

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Section: Resultsmentioning

confidence: 82%

Sulfheme formation during homocysteine S-oxygenation by catalase in cancers and neurodegenerative diseases

et al. 2016

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“…Thiophene is a privileged scaffold widely found in biologically active compounds and functional materials . Although transition‐metal‐catalyzed approaches have been extensively developed to achieve diverse heterocycle syntheses under neutral conditions, the catalytic synthesis of substituted thiophenes is underdeveloped because organosulfur compounds often inhibit the catalytic turnover by strong coordination of the soft sulfur atom to the transition‐metal catalysts …”

Section: Figurementioning

confidence: 70%

Catalytic [2+2+1] Synthesis of Fused Thiophenes Using Thiocarbonyls as Sulfur Donors

2016

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The use of N-(p-chlorophenyl)methylbenzoxazole-2-thione as asulfur-atom donor enables the catalytic [2+ +2+ +1] cycloaddition of diynes in wet DMF at 80 8 8Cwhen open to air, thus affording diverse fused thiophenes with good yields and wide functional-group compatibility.Ap lausible mechanism, involving ac ationic ruthenacycle intermediate,w as also proposed on the basis of several control experiments.Supportinginformation for this article can be found under: http://dx.

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“…Heterocycles containing 1,2,3-triazole and thiophene moieties have a wide range of applications (Dheer et al, 2017;Jiang & Kuang, 2013;Li et al, 2016;Mancuso & Gabriele, 2014;Shafran et al, 2008;Yamada et al, 2018). As part of our studies in this area, we now describe the crystal structure of the title compound.…”

Section: Structure Descriptionmentioning

confidence: 99%

1-{2-Anilino-4-methyl-5-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carbonyl]thiophen-3-yl}ethanone

et al. 2018

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In the title compound, C24H22N4O2S, the dihedral angle between the triazole and thiophene rings is 4.83 (14)°. The dihedral angles between the triazole and tolyl rings and between the thiophene and phenyl rings are 48.42 (16) and 9.23 (13)°, respectively. An intramolecular N—H...O hydrogen bond closes anS(6) loop. In the crystal, molecules are stacked parallel to thea-axis direction with weak π–π interactions between adjacent thiophenyl and triazolyl groups within the stack [centroid–centroid separation = 3.9811 (16) Å].

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Recent Advances in the Synthesis of Thiophene Derivatives by Cyclization of Functionalized Alkynes

Abstract: This review is intended to highlight some recent and particularly interesting examples of the synthesis of thiophene derivatives by heterocyclization of readily available S-containing alkyne substrates.

Cited by 80 publications

References 106 publications

Sulfheme formation during homocysteine S-oxygenation by catalase in cancers and neurodegenerative diseases

Sulfheme formation during homocysteine S-oxygenation by catalase in cancers and neurodegenerative diseases

Catalytic [2+2+1] Synthesis of Fused Thiophenes Using Thiocarbonyls as Sulfur Donors

1-{2-Anilino-4-methyl-5-[5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carbonyl]thiophen-3-yl}ethanone

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