scholarly journals The Fluoride Anion-Catalyzed Sulfurization of Thioketones with Elemental Sulfur Leading to Sulfur-Rich Heterocycles: First Sulfurization of Thiochalcones

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 822
Author(s):  
Grzegorz Mlostoń ◽  
Jakub Wręczycki ◽  
Katarzyna Urbaniak ◽  
Dariusz M. Bieliński ◽  
Heinz Heimgartner
Keyword(s):  
Elemental Sulfur ◽  
Fluoride Anion ◽  
Ring Size ◽  
Mild Conditions ◽  
Tetrabutylammonium Fluoride ◽  
Cesium Fluoride ◽  
Secondary Reactions ◽  
Derivatives Of

Fluoride anion was demonstrated as a superior activator of elemental sulfur (S8) to perform sulfurization of thioketones leading to diverse sulfur-rich heterocycles. Due to solubility problems, reactions must be carried out either in THF using tetrabutylammonium fluoride (TBAF) or in DMF using cesium fluoride (CsF), respectively. The reactive sulfurizing reagents are in situ generated, nucleophilic fluoropolysulfide anions FS(8−x)−, which react with the C=S bond according to the carbophilic addition mode. Dithiiranes formed thereby, existing in an equilibrium with the ring-opened form (diradicals/zwitterions) are key-intermediates, which undergo either a step-wise dimerization to afford 1,2,4,5-tetrathianes or an intramolecular insertion, leading in the case of thioxo derivatives of 2,2,4,4-tetramethylcyclobutane-1,3-dione to ring enlarged products. In reactions catalyzed by TBAF, water bounded to fluoride anion via H-bridges and forming thereby its stable hydrates is involved in secondary reactions leading, e.g., in the case of 2,2,4,4-tetramethyl-3-thioxocyclobutanone to the formation of some unexpected products such as the ring enlarged dithiolactone and ring-opened dithiocarboxylate. In contrast to thioketones, the fluoride anion catalyzed sulfurization of their α,β-unsaturated analogues, i.e., thiochalcones is slow and inefficient. However, an alternative protocol with triphenylphosphine (PPh3) applied as a catalyst, offers an attractive approach to the synthesis of 3H-1,2-dithioles via 1,5-dipolar electrocyclization of the in situ-generated α,β-unsaturated thiocabonyl S-sulfides. All reactions occur under mild conditions and can be considered as attractive methods for the preparation of sulfur rich heterocycles with diverse ring-size.

Efficient Synthesis of Diverse 5-Thio- or 5-Selenotriazoles: One-Pot Multicomponent Reaction from Elemental Sulfur or Selenium

Synthesis ◽  
2019 ◽  
Vol 51 (22) ◽  
pp. 4170-4182 ◽  
Author(s):  
Lin-Lin Zhang ◽  
Ya-Ting Li ◽  
Ting Gao ◽  
Sha-Sha Guo ◽  
Bei Yang ◽  
...  
Keyword(s):  
Elemental Sulfur ◽  
Functional Group ◽  
High Efficiency ◽  
Efficient Synthesis ◽  
One Pot ◽  
Mild Conditions ◽  
Ligand Free ◽  
Multistep Reaction ◽  
Easy Operation

A sequential multistep reaction toward 5-thio- or 5-selenotriazoles has been established by generation of both copper(I) triazolides and sulfenylating or selenylating agents in situ, starting from elemental sulfur or selenium. This reaction features mild conditions, readily available and broad-scope substrates, good functional group compatibility, high efficiency and regioselectivity, easy operation, and ligand-free CuI.

Cleavage of the Epimines of 1,6-Anhydrohexoses with Fluoride Anion

2005 ◽  
Vol 70 (12) ◽  
pp. 2075-2085 ◽  
Author(s):  
Jiří Kroutil ◽  
Klára Jeništová
Keyword(s):  
Fluoride Anion ◽  
Ring Cleavage ◽  
Protecting Group ◽  
Reaction Conditions ◽  
Aziridine Ring ◽  
Cleavage Reactions ◽  
Derivatives Of ◽  
Fluoro Derivatives

Aziridine ring cleavage reactions of five N-nosylepimines (2-6) having D-talo, D-galacto, D-manno, and D-allo configurations with potassium hydrogendifluoride under various reaction conditions have been performed. The cleavage regioselectively afforded diaxial isomers of vicinal amino-fluoro derivatives of 1,6-anhydro-β-D-gluco- and mannopyranose 7-11 in 51-94% yields. Removal of 2-nitrobenzenesulfonyl protecting group with benzenethiol has been attempted in the case of compound 10.

scholarly journals Enzymatic synthesis and phosphorolysis of 4(2)-thioxo- and 6(5)-azapyrimidine nucleosides by E. coli nucleoside phosphorylases

2016 ◽  
Vol 12 ◽  
pp. 2588-2601 ◽  
Author(s):  
Vladimir A Stepchenko ◽  
Anatoly I Miroshnikov ◽  
Frank Seela ◽  
Igor A Mikhailopulo
Keyword(s):  
Purine Nucleoside Phosphorylase ◽  
Reaction Conditions ◽  
E Coli ◽  
No Formation ◽  
Structural Peculiarities ◽  
Substrate Properties ◽  
Nucleoside Phosphorylases ◽  
Derivatives Of

The trans-2-deoxyribosylation of 4-thiouracil (4SUra) and 2-thiouracil (2SUra), as well as 6-azauracil, 6-azathymine and 6-aza-2-thiothymine was studied using dG and E. coli purine nucleoside phosphorylase (PNP) for the in situ generation of 2-deoxy-α-D-ribofuranose-1-phosphate (dRib-1P) followed by its coupling with the bases catalyzed by either E. coli thymidine (TP) or uridine (UP) phosphorylases. 4SUra revealed satisfactory substrate activity for UP and, unexpectedly, complete inertness for TP; no formation of 2’-deoxy-2-thiouridine (2SUd) was observed under analogous reaction conditions in the presence of UP and TP. On the contrary, 2SU, 2SUd, 4STd and 2STd are good substrates for both UP and TP; moreover, 2SU, 4STd and 2’-deoxy-5-azacytidine (Decitabine) are substrates for PNP and the phosphorolysis of the latter is reversible. Condensation of 2SUra and 5-azacytosine with dRib-1P (Ba salt) catalyzed by the accordant UP and PNP in Tris∙HCl buffer gave 2SUd and 2’-deoxy-5-azacytidine in 27% and 15% yields, respectively. 6-Azauracil and 6-azathymine showed good substrate properties for both TP and UP, whereas only TP recognizes 2-thio-6-azathymine as a substrate. 5-Phenyl and 5-tert-butyl derivatives of 6-azauracil and its 2-thioxo derivative were tested as substrates for UP and TP, and only 5-phenyl- and 5-tert-butyl-6-azauracils displayed very low substrate activity. The role of structural peculiarities and electronic properties in the substrate recognition by E. coli nucleoside phosphorylases is discussed.

scholarly journals Pyrobaculum yellowstonensis Strain WP30 Respires on Elemental Sulfur and/or Arsenate in Circumneutral Sulfidic Geothermal Sediments of Yellowstone National Park

2015 ◽  
Vol 81 (17) ◽  
pp. 5907-5916 ◽  
Author(s):  
Z. J. Jay ◽  
J. P. Beam ◽  
A. Dohnalkova ◽  
R. Lohmayer ◽  
B. Bodle ◽  
...  
Keyword(s):  
Yellowstone National Park ◽  
National Park ◽  
Elemental Sulfur ◽  
De Novo ◽  
Hot Spring ◽  
Content Type ◽  
Physiological Attributes ◽  
And Function ◽  
Metagenome Sequence

ABSTRACTThermoproteales(phylumCrenarchaeota) populations are abundant in high-temperature (>70°C) environments of Yellowstone National Park (YNP) and are important in mediating the biogeochemical cycles of sulfur, arsenic, and carbon. The objectives of this study were to determine the specific physiological attributes of the isolatePyrobaculum yellowstonensisstrain WP30, which was obtained from an elemental sulfur sediment (Joseph's Coat Hot Spring [JCHS], 80°C, pH 6.1, 135 μM As) and relate this organism to geochemical processes occurringin situ. Strain WP30 is a chemoorganoheterotroph and requires elemental sulfur and/or arsenate as an electron acceptor. Growth in the presence of elemental sulfur and arsenate resulted in the formation of thioarsenates and polysulfides. The complete genome of this organism was sequenced (1.99 Mb, 58% G+C content), revealing numerous metabolic pathways for the degradation of carbohydrates, amino acids, and lipids. Multiple dimethyl sulfoxide-molybdopterin (DMSO-MPT) oxidoreductase genes, which are implicated in the reduction of sulfur and arsenic, were identified. Pathways for thede novosynthesis of nearly all required cofactors and metabolites were identified. The comparative genomics ofP. yellowstonensisand the assembled metagenome sequence from JCHS showed that this organism is highly related (∼95% average nucleotide sequence identity) toin situpopulations. The physiological attributes and metabolic capabilities ofP. yellowstonensisprovide an important foundation for developing an understanding of the distribution and function of these populations in YNP.

A new approach to arylhydrazides via the reaction of the Mitsunobu reagent with arynes: further application to access diverse nitrogen-containing heterocycles in one pot

2017 ◽  
Vol 4 (8) ◽  
pp. 1636-1639 ◽  
Author(s):  
Bin Cheng ◽  
Bian Bao ◽  
Yanhe Chen ◽  
Ning Wang ◽  
Yun Li ◽  
...  
Keyword(s):  
One Pot ◽  
New Approach ◽  
Mild Conditions ◽  
Highly Active ◽  
Active Intermediates

A new route to arylhydrazides involving the reaction of two highly active intermediates, the 1,3-zwitterion generated in situ from the Mitsunobu reagent and arynes, under mild conditions has been developed.

scholarly journals Ultra-Small Pd(0) Nanoparticles into a Designed Semisynthetic Lipase: An Efficient and Recyclable Heterogeneous Biohybrid Catalyst for the Heck Reaction under Mild Conditions

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2358 ◽  
Author(s):  
David Lopez-Tejedor ◽  
Blanca de las Rivas ◽  
Jose M. Palomo
Keyword(s):  
Catalytic Activity ◽  
Protein Structure ◽  
Heck Reaction ◽  
Catalytic Performance ◽  
Reducing Agent ◽  
Chemically Modified ◽  
Mild Conditions ◽  
In Situ Formation ◽  
Geobacillus Thermocatenulatus

A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically modified by the introduction of a tailor-made cysteine-containing complementary peptide- was used as the stabilizing and reducing agent for the in situ formation of ultra-small PdNPs nanoparticles embedded on the protein structure. This bionanohybrid was an excellent catalyst in the synthesis of trans-ethyl cinnamate by Heck reaction at 65 °C. It showed the best catalytic performance in dimethylformamide (DMF) containing 10–25% of water as a solvent but was also able to catalyze the reaction in pure DMF or with a higher amount of water as co-solvent. The recyclability and stability were excellent, maintaining more than 90% of catalytic activity after five cycles of use.

scholarly journals Thermodynamically stable [4 + 2] cycloadducts of lanthanum-encapsulated endohedral metallofullerenes

2014 ◽  
Vol 10 ◽  
pp. 714-721 ◽  
Author(s):  
Yuta Takano ◽  
Yuki Nagashima ◽  
M Ángeles Herranz ◽  
Nazario Martín ◽  
Takeshi Akasaka
Keyword(s):  
Thermal Stability ◽  
Material Science ◽  
Molecular Structures ◽  
Spectroscopic Methods ◽  
Dynamic Nmr ◽  
The Novel ◽  
Endohedral Metallofullerenes ◽  
Derivatives Of ◽  
Paramagnetic Properties

The [4 + 2] cycloaddition of o-quinodimethanes, generated in situ from the sultine 4,5-benzo-3,6-dihydro-1,2-oxathiin 2-oxide and its derivative, to La metal-encapsulated fullerenes, La2@C80 or La@C82, afforded the novel derivatives of endohedral metallofullerenes (3a,b, 4a,b and 5b). Molecular structures of the resulting compounds were elucidated using spectroscopic methods such as MALDI–TOF mass, optical absorption, and NMR spectroscopy. The [4 + 2] adducts of La2@C80 (3a,b, and 4a,b) and La@C82 (5b), respectively, retain diamagnetic and paramagnetic properties, as confirmed by EPR spectroscopy. Dynamic NMR measurements of 4a at various temperatures demonstrated the boat-to-boat inversions of the addend. In addition, 5b revealed remarkable thermal stability in comparison with the reported [4 + 2] cycloadduct of pentamethylcyclopentadiene and La@C82 (6). These findings demonstrate the utility of sultines to afford thermodynamically stable endohedral metallofullerene derivatives for the use in material science.

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