Experimental and Theoretical Study of the Keto–Enol Tautomerization of 3,5‐Dioxopimelates

Erfle, Silke; Reim, Stefanie; Michalik, Dirk; Jiao, Haijun; Langer, Peter

doi:10.1002/ejoc.201100292

Cited by 8 publications

(4 citation statements)

References 21 publications

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“…Keto–enol tautomerization also plays essential roles in combustion and atmospheric chemistry due to the different reactivity of tautomers. ,,, The importance of enol tautomers as significant intermediates is recognized even for flame chemistry. , The keto tautomer is typically strongly favored, especially in polar liquids (see, e.g., refs ,,, ). This is due to the higher polarity of the keto form in such liquids.…”

Section: Resultsmentioning

confidence: 99%

“…Such species were also observed in the troposphere, cool flames, and other combustion processes. ,, Perhaps, the sequential CHAT mechanism can also serve as a new pathway to the formation of poly hydroxides that are abundant in combustion media, particularly at elevated temperatures. There are also a variety of multicarbonyl natural products, such as alkyl malonates and poly(β-oxo)carboxylic acids (polyketides) important for pharmacology, for which keto–enol tautomerization is a key issue (see, e.g., ref ). Enzymes could also perhaps employ lower-energy versions of this mechanism along with benefits of ions and solvents supported by low-temperature tunneling effects.…”

Section: Resultsmentioning

confidence: 99%

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Intramolecular Catalytic Hydrogen Atom Transfer (CHAT)

Asatryan,

Hudzik,

Swihart

2024

J. Phys. Chem. A

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Intramolecular catalysis (IntraCat) is the acceleration of a process at one site of a molecule catalyzed by a functional group in the same molecule; an external agent such as a solvent typically facilitates it. Here, we report a general first-principles-based IntraCat mechanism, which strictly occurs within a single molecule with no coreagent being involved�we call it intramolecular catalytic transfer of hydrogen atoms (CHAT). A reactive part of a molecule (chat catalyst moiety or chat agent, represented by −OOH, −COOH, −SH, −CH 2 OH, −HPO 4 , or another bifunctional Hdonor/acceptor group) catalyzes an interconversion process, such as keto−enol or amino−imino tautomerization, and cyclization in the same molecule, while being regenerated in the process. It can thus be regarded as an intramolecular version of the intermolecular H atom transfer processes mediated by an external molecular catalyst, e.g., dihydrogen, water, or a carboxylic acid. Earlier, we proposed a general mechanistic systematization of intermolecular processes, illustrated in the simplest case of the H 2 -mediated reactions classified as dihydrogen catalysis [

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Intramolecular Catalytic Hydrogen Atom Transfer (CHAT)

Asatryan,

Hudzik,

Swihart

2024

J. Phys. Chem. A

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“…Later, the scope was extended to other nonsymmetrical derivatives. 23 Scheme 15 Tautomerism of 25a-j.…”

Section: Methyl Malonyl Chloridementioning

confidence: 99%

“…The formation of the latter can be explained by insertion of benzyne into the central carbon-carbon bond of 25a to give intermediate A and subsequent intramolecular aldol condensation. 34…”

Section: Reaction With Benzynementioning

confidence: 99%

Synthesis and Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds

Langer

2021

Synlett

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The reaction of 1,3-bis(silyloxy)-1,3-butadienes with functionalized and nonfunctionalized acid chlorides and bis(acid chlorides) gives rise to the formation of a great variety of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds and cyclic products derived from them. Examples include functionalized and nonfunctionalized 3,5-dioxopentanoates, 3,5-dioxopimelates, 3-alkylidene-3H-isobenzofuran-1-ones, salicylates, 3(2H)furanones, and 3-oxo-4-sulfonylesters. Methylation and cyclopropanation reactions of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds do not provide access to the expected permethylated and cyclopropanated polycarbonyl compounds. However, the latter could be prepared by stepwise protocols. The reaction of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds with dinucleophiles resulted in cyclization reactions to give a variety of heterocyclic structures.1 Introduction2 Reactions of 1,3-Bis(silyloxy)-1,3-butadienes with Acid Chlorides3 Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds4 Conclusion

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Synthesis and Structures of Fluoroalkylated Triketides

et al. 2011

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The synthesis and structures of fluoroalkylated triketides (3,5-dioxo esters) and 1,3,5-triketones -such as 1,1,1-trifluoroheptane-2,4,6-dione -were studied. The synthesis is based on reactions between 1,3-dicarbonyl dianions and esters. In CDCl 3 , the fluoroalkylated triketides exclusively exist in the forms of enol tautomers. In [D 6 ]DMSO, equilibria between enols and keto hydrates, formed by addition of water to the

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Experimental and Theoretical Study of the Keto–Enol Tautomerization of 3,5‐Dioxopimelates

Cited by 8 publications

References 21 publications

Intramolecular Catalytic Hydrogen Atom Transfer (CHAT)

Intramolecular Catalytic Hydrogen Atom Transfer (CHAT)

Synthesis and Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds

Synthesis and Structures of Fluoroalkylated Triketides

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