Preparation of 2,5-anhydrohexitols (part I). Silicon-directed stereocontrolled cyclization

Article abstract of DOI:10.1080/07328309908543989

Stereoselective chain-extension of carbohydrate aldehydes with the hydroxymethylating reagent (dimethylphenylsilyl)methylmagnesium chloride (1) followed by acid-mediated cyclization gives access to 2,5-anhydro-hexitols. The stereoselectivity of the ring closure depends on the nature of the acid, i.e., treatment with excess BF₃·Et₂O or catalytic H₂SO₄ leads to tetrahydrofurans with 2,3-cis or 2,3-trans configuration, respectively. Concomitant elimination is effectively suppressed in case of cyclisation of the more sterically hindered isopropyl substituted silanes.

Full text of DOI:10.1080/07328309908543989

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Journal of Carbohydrate Chemistry
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Preparation of 2,5-Anhydrohexitols
(Part I). Silicon-Directed
Stereocontrolled Cyclization
Floris L. van Delft , A. Rob , P.M. Valentijn , Gijs A. van der
Marel & Jacques H. van Boom
a Gorlaeus Laboratories , Leiden Institute of Chemistry , P.O.
Box 9502, 2300 RA, Leiden, The Netherlands
Published online: 27 Feb 2008.
To cite this article: Floris L. van Delft , A. Rob , P.M. Valentijn , Gijs A. van der Marel &
Jacques H. van Boom (1999) Preparation of 2,5-Anhydrohexitols (Part I). Silicon-Directed
Stereocontrolled Cyclization, Journal of Carbohydrate Chemistry, 18:2, 165-190, DOI:
10.1080/07328309908543989
To link to this article: http://dx.doi.org/10.1080/07328309908543989
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