ChemInform Abstract: Cycloaddition Reactions of Hexafluorothioacetone and Halogenated Thiocarbonyl Compounds - Chemical Transformations of Fluorinated Sulfur-Containing Heterocycles

The [2+2+2] cycloaddition reaction is a useful tool to realize unusual chemical transformations which are not achievable by traditional methods. Here, we report our work during the past two decades that involve utilization of transition-metal complexes in a [2+2+2] cyclotrimerization reaction. Several key “building blocks” were assembled by a [2+2+2] cycloaddition approach and they have been further expanded by other synthetic transformations to design unusual amino acids and peptides, diphenylalkanes, bis- and trisaryl benzene derivatives, annulated benzocycloalkanes, spirocycles, and spirooxindole derivatives. Furthermore, we have also discussed about alkyne surrogates, environmentally friendly, and stereoselective [2+2+2] cycloaddition reactions. Application of the [2+2+2] cycloaddition reaction in total synthesis is also covered. In this review we also included others work to give a balanced view of the recent developments in the area of [2+2+2] cycloaddition.1 Introduction2 Unusual Amino Acids and Peptides3 Heteroanalogues of Indane4 Diphenylalkane Derivatives5 Multi-Armed Aryl Benzene Derivatives6 Annulated Benzocycloalkanes7 Spirocycles8 Selectivity in [2+2+2] Cycloaddition of Alkynes9 [2+2+2] Cycloaddition Reactions under Environmentally Friendly Conditions10 Alkyne Surrogates11 Domino Reactions involving a [2+2+2] Cycloaddition12 Biologically Important Targets/Total Synthesis13 Conclusions

Download Full-text

Polyfunctional macroheterocycles. 4. Synthesis and some chemical transformations of nitrogen- and sulfur-containing crown compounds with exocyclic methoxycarbonyl, cyano, and phenylethyl groups

Chemistry of Heterocyclic Compounds ◽

10.1007/bf00473951 ◽

1992 ◽

Vol 28 (2) ◽

pp. 228-231

Author(s):

M. G. Voronkov ◽

V. I. Knutov ◽

M. K. Butin

Keyword(s):

Crown Compounds ◽

Chemical Transformations ◽

Sulfur Containing

Download Full-text

Synthesis and Reactivity of Electron-Deficient 3-Vinylchromones

SynOpen ◽

10.1055/a-1589-9556 ◽

2021 ◽

Vol 05 (03) ◽

pp. 255-277

Author(s):

Vyacheslav Y. Sosnovskikh

Keyword(s):

Double Bond ◽

Chemical Properties ◽

Building Blocks ◽

High Reactivity ◽

Cycloaddition Reactions ◽

Chemical Transformations ◽

Pyrone Ring ◽

The Past ◽

Palladium Catalyzed ◽

First Time

AbstractThe reported methods and data for the synthesis and reactivity of electron-deficient 3-vinylchromones containing electron-withdrawing groups at the exo-cyclic double bond are summarized and systematized for the first time. The main methods for obtaining these compounds are Knoevenagel condensation, Wittig reaction, and palladium-catalyzed cross-couplings. The most important chemical properties are transformations under the action of mono- and dinucleophiles, ambiphilic cyclizations, and cycloaddition reactions. The cross-conjugated and polyelectrophilic dienone system in 3-vinylchromones provides their high reactivity and makes these compounds valuable building blocks for the preparation of more complex heterocyclic systems. Chemical transformations of 3-vinylchromones usually begin with an attack of the C-2 atom and are accompanied by the opening of the pyrone ring followed by recyclization, in which the carbonyl group of chromone, an exo-double bond or a substituent on it can take part. The mechanisms of the reactions are discussed, the conditions for their implementation are described, and the yields of the resulting products are given. This review focuses on an analysis and generalization of the knowledge that has accumulated on the chemistry of electron-deficient 3-vinylchromones, mostly over the past 15 years.1 Introduction2 Synthesis of 3-Vinylchromones3 Reactions with Mononucleophiles4 Reactions with Dinucleophiles5 Ambiphilic Cyclization6 Cycloaddition Reactions7 Other Reactions8 Conclusion

Download Full-text

Reductive Stress of Sulfur-Containing Amino Acids within Proteins and Implication of Tandem Protein–Lipid Damage

International Journal of Molecular Sciences ◽

10.3390/ijms222312863 ◽

2021 ◽

Vol 22 (23) ◽

pp. 12863

Author(s):

Chryssostomos Chatgilialoglu ◽

Carla Ferreri

Keyword(s):

The Other ◽

Aminobutyric Acid ◽

Chemical Transformations ◽

Hydrogen Atoms ◽

Unsaturated Lipids ◽

Hydrated Electrons ◽

Chemistry Modeling ◽

Lipid Damages ◽

The Stability ◽

Sulfur Containing

Reductive radical stress represents the other side of the redox spectrum, less studied but equally important compared to oxidative stress. The reactivity of hydrogen atoms (H•) and hydrated electrons (e–aq) connected with peptides/proteins is summarized, focusing on the chemical transformations of methionine (Met) and cystine (CysS–SCys) residues into α-aminobutyric acid and alanine, respectively. Chemical and mechanistic aspects of desulfurization processes with formation of diffusible sulfur-centered radicals, such as methanethiyl (CH3S•) and sulfhydryl (HS•) radicals, are discussed. These findings are further applied to biomimetic radical chemistry, modeling the occurrence of tandem protein–lipid damages in proteo-liposomes and demonstrating that generation of sulfur-centered radicals from a variety of proteins is coupled with the cis–trans isomerization of unsaturated lipids in membranes. Recent applications to pharmaceutical and pharmacological contexts are described, evidencing novel perspectives in the stability of formulations and mode of action of drugs, respectively.

Download Full-text