Реферат: Finding convenient ways for the stereoselective α-sialylation is important due to the high practical significance of α-sialic acid-containing glycans and neoglycoconjugates. It was proposed that sialylation stereoselectivity is determined by the structure of the sialyl cation (also known in biochemistry as “sialosyl cation”), a supposed intermediate in this reaction. Here we design a new approach for studying the conformational space of highly flexible sialyl cation and find 1625 unique conformers including those stabilized by covalent remote participation (also known as long-range participation) of 4-O-acetyl (4-OAc), 5-N-trifluoroacetyl (5-NTFA), as well as 7,8,9-OAc from both α and β sides. The most energetically stable sialyl cation conformers are featured by 4-OAc participation, closely followed by 5-NTFA- and 7-OAc-stabilized conformers; unstabilized sialyl cation conformers are ∼10 kcal mol−1 less stable than the 4-OAc-stabilized ones. Analysis of all the obtained conformers by means of substituents positions, side chain conformations and ring puckering led us to a new “eight-conformer hypothesis” which describes interconversions among the most important sialyl cation conformers and predicts that stronger remote participation of acyl groups favors β-anomers. Thus, selective synthesis of the desired α-sialosides requires minimization of acyl groups participation.

Библиографическая ссылка: Panova M.V. , Medvedev M.G. , Orlova A.V. , Kononov L.
Exhaustive Conformational Search for Sialyl Cation Reveals Possibility of Remote Participation of Acyl Groups
ChemPhysChem. 2021. V.23. N3. e202100788 . DOI: 10.1002/cphc.202100788 WOS Scopus OpenAlex

Идентификаторы БД:

Web of science:	WOS:000730668200001
Scopus:	2-s2.0-85121344370
OpenAlex:	W3215660167

Цитирование в БД:

БД	Цитирований
OpenAlex	9
Scopus	8
Web of science	8

Альметрики: