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Synlett 2022; 33(05): 473-477
DOI: 10.1055/a-1730-9458
letter

Trifluoroacetic Acid Promoted Ring Contraction in 2,3-Di-O-silylated O-Galactopyranosides and Hemiacetals

Polina I. Abronina∗
,
Nelly N. Malysheva
,
Alexander I. Zinin
,
Maxim Y. Karpenko
,
Natalya G. Kolotyrkina
,
Leonid O. Kononov  ∗
This work was financially supported by the Russian Foundation for Basic Research (20-03-00465-a).
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Abstract

A pyranose ring contraction of 2,3-di-O-silylated O-galactopyranosides with retention of aglycone promoted by anhydrous trifluoroacetic acid (TFA) in CH2Cl2 was demonstrated for the first time. In addition, TFA-promoted pyranose ring contraction of 2,3-bis-O-(triisopropylsilyl)-d-galactopyranose with formation of the corresponding anomeric triols in furanose form was successfully performed. A representative series of β-d-galactopyranosides with Me, Bn, allyl, or 3-(trifluoroacetamido)propyl aglycones has been investigated. TBDPS protective groups were found to be more stable than TIPS groups under conditions of TFA-promoted pyranose ring contraction. An easy access to 2,3-di-O-TBDPS-substituted allyl and benzyl galactofuranosides and 2,3-bis-O-(triisopropylsilyl)-β-d-galactofuranose may present an advantage in synthesis of selectively protected monosacharide building blocks, useful for the synthesis of biologically important oligosaccharides.

Key words

carbohydrates - protecting groups - synthetic methods

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1730-9458. Included are experimental procedures and full characterization data for all new compounds, and copies of NMR spectra for all new compounds (PDF).
  • Supporting Information


Publication History

Received: 11 November 2021

Accepted after revision: 04 January 2022

Accepted Manuscript online:
04 January 2022

Article published online:
28 January 2022

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