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. 2010 Oct 15;12(20):4624-7.
doi: 10.1021/ol1019629.

Stereoselective C-glycosidations with achiral and enantioenriched allenylsilanes

Ryan A Brawn  1 , James S Panek
Affiliations

Stereoselective C-glycosidations with achiral and enantioenriched allenylsilanes

Ryan A Brawn et al. Org Lett. .

Erratum in

  • Org Lett. 2010 Dec 3;12(23):5600

Abstract

Allenylsilanes are used as carbon nucleophiles in highly stereoselective Lewis acid-promoted C-glycosidations, resulting in the introduction of an internal alkyne with an adjacent stereocenter. Both achiral and chiral allenylsilanes form the desired products with high diastereoselectivity, where the nucleophile adds exclusively to the α-face of the intermediate oxonium ion. Reactions with glucal and galactal afford dihydropyran products, while reactions with a ribose derivative yield dihydrofuran products.

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Figures

Scheme 1
Scheme 1
Additions of Silane Nucleophiles to Glucal
Scheme 2
Scheme 2
Additions of Enantioenriched Allenylsilanes to Tri-O-acetyl-D-glucal and galactala a.Reaction conditions: TMSOTf (1.0 equiv) was added to a solution of allenylsilane (1.0 equiv) and carbohydrate (1.2 equiv) in MeCN (0.5 M) at −40 °C and stirred for 1 hour. b. Isolated yields after chromatographic purification. Diastereomeric ratios determined by 1H NMR analysis of crude material.
Scheme 3
Scheme 3
Synthesis of Dihydrofuran 7 a.Isolated yield after chromatographic purification.
Scheme 4
Scheme 4
Additions of Chiral Allenysilanes to Dihydrofuran 7 a.Isolated yield after chromatographic purification. Diastereomeric ratios determined by 1H NMR analysis of crude material.
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