Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity

Molecules

Jarosław Błaszczyk¹  Bogdan Bujnicki¹  Józef Drabowicz¹  Marek Chmielewski² 

[1] Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Division of Organic Chemistry, Sienkiewicza 112, 90–363 Łódź, Poland;Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01–224 Warszawa, Poland;

关键词: diastereoisomeric sulfites and sulfinates;    sulfinylation;    crystal structure;    X-ray crystallography;    single-crystal diffractometry;    absolute configuration;   

DOI  :  10.3390/molecules25153392

来源: DOAJ

【 摘 要 】

The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P2₁2₁2₁, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.

【 授权许可】

Unknown