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Inne
Internal hydrogen bond influences the formation of [2+2] Schiff base macrocycle: open-chain vs. hemiaminal and macrocycle forms.
Autorzy
Rok wydania
2019
Czasopismo
European Journal of Organic Chemistry
Strony
2243-2252
DOI
10.1002/ejoc.201801811
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Open‐chain vs. hemiaminal and macrocycle forms of the condensation product of 2,6‐diformylpyridine and opposite enantiomers of trans‐1,2‐diaminocyclopentane have been studied using DFT methods to reveal that the macrocycle (with a water molecule co‐product) is the thermochemically preferred form. The mechanistic picture of formation of [[2+2]] Schiff base macrocycle from its chain precursor has been supplemented with the electron localization function analysis revealing the crucial electronic aspects underlying the covalent bonds evolution. The macrocycle formation may proceed along two paths, through two distinct diastereoisomerc hemiaminal intermediates. The reaction rate limiting water elimination step exhibits the considerably lower and unusually flat energy barrier for the path involving S hemiaminal due to the strong decoupling of the CO bond cleavage from the proton migration to form the water molecule.
Słowa kluczowe
molecule, 6-Diformylpyridine, trans-1, 2-Diaminocyclopentane, trans-1, 2-Diaminocyclohexane, Chirality, Electron localization function (ELF)
Adres publiczny
https://doi.org/10.1002/ejoc.201801811
Strona internetowa wydawcy
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