Abstract: Acid-promoted rearrangement of a series of 1-thio-α/β-d-galactopyranosides with bulky triisopropylsilyl (TIPS) or tert-butyldiphenylsilyl (TBDPS) groups at both O-2 and O-3 and bearing various substituents at the S atom in anomeric position leading to ring contraction has been studied. The reaction rates of pyranose ring contraction in S-galactopyranosides were found to be strongly influenced by anomeric configuration and aglycone structure. Ethyl 1-thio-β-d-galactopyranosides underwent ring contraction faster than ethyl 1-thio-α-d-thiogalactopyranosides. 1-Thio-β-d-galactopyranosides with TIPS groups bearing electron-donating 5-tert-butyl-2-methylphenyl group in aglycone could be involved into rearrangement to furanosides under milder acidic conditions (aq TFA in CH2Cl2) than the corresponding 1-thio-β-d-galactopyranosides with phenyl or 4-chlorophenyl groups in aglycone (anhydrous TFA in CH2Cl2). On the contrary, 1-thio-β-d-thiogalactopyranoside bearing electron-withdrawing 4-nitrophenyl group in aglycone did not undergo ring contraction under identical conditions.

Cite: Abronina P.I. , Zinin A.I. , Malysheva N.N. , Karpenko M.Y. , Kolotyrkina N.G. , Kononov L.O.
The Influence of Anomeric Configuration and Aglycone Structure on the Outcome of Acid‐Promoted Ring Contraction in 2,3‐Di‐O‐Silylated S‐Galactopyranosides
ChemistrySelect. 2021. V.6. N24. P.6223-6229. DOI: 10.1002/slct.202101441 WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:000674320500048
Scopus:	2-s2.0-85110728409
OpenAlex:	W3176626155

Citing:

DB	Citing
OpenAlex	5
Scopus	5
Web of science	6

Altmetrics: