Catalysis by mercuric ion of reactions of glycals with water

doi:10.1016/S0008-6215(00)84269-X

Carbohydrate Research

Volume 42, Issue 2, July 1975, Pages 267-274

https://doi.org/10.1016/S0008-6215(00)84269-X Get rights and content

Abstract

In the presence of mercuric sulfate, 3,4,6-tri-O-acetyl-d-glucal (4), dissolved in 1,4-dioxane-dilute sulfuric acid at room temperature, is rapidly and quantitatively converted into 4,6-di-O-acetyl-2,3-dideoxy-aldelhydod-erythro-trans-hex-2-enose (8). With acetone as the organic component of the solvent, this product is accompanied by the 5,6-di-O-acetyl isomer (10). The corresponding, α,β-unsaturated aldehydes (12 and 13; 15) are formed in an analogous way from 3,4,6-tri-O-acetyl-d-galactal (11) and 3,4-di-O-acetyl-d-arabinal (14). Similarly, instead of hydration, d-glucal (1) and d-galactal undergo elimination catalyzed by mercuric ion and acid to yield 2-(d-glycero-1,2-dihydroxyethyl)furan (3) as the sole product. Possible mechanisms for these transformations are discussed.

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A metal free synthesis of enantiopure 2,3-dideoxy-α, β-unsaturated carbohydrate enals (Perlin aldehydes), in CH₃CN-0.02 N H₂SO₄ in water (1:1, v/v) with 0.5 equivalent additives (4-hydroxy-6-methyl-2-pyrone or 4-amino coumarin), has been reported. This efficient protocol works well for the acetylated glycals (glucal, galactal and arabinal) and afforded Perlin aldehydes and hemiacetals in acceptable to good yields. Whereas, benzylated glycals furnished respective Perlin aldehydes, hemiacetals and the 2-deoxy derivatives, under similar reaction conditions. The products yields were significantly reduced when the additives were removed from the reaction mixture, indicating that they constitute an essential component of this approach. Further the use of 0.02 N H₂SO₄ in water: acetonitrile (1:1, v/v) solvent system is essential for the formation of Perlin aldehydes. The similar reactions under neutral reaction conditions (CH₃CN:H₂O, 1:1, v/v) with additives, afforded the hemiacetals as major product. This methodology is a metal free approach to Perlin aldehyde synthesis and therefore having additional benefit of its use in preparation of bioactive drug molecules, where metal toxicity is the major concern.
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Examples of such compounds include alkyl-hex-2-eno-uloses,2 2-C-formyl glycals,3 2,3-dideoxy-α,β-unsaturated sugar aldehydes4,5 and other carbohydrate based enones.6 Since last three decades, 2,3-dideoxy-α,β-unsaturated sugar aldehydes, popularly known as Perlin aldehydes, have been serving as attractive precursors for the synthesis of a wide array of biologically important natural and unnatural compounds.7–20 Conventionally, Perlin aldehydes are prepared by oxymercuration–demercuration reaction of suitably protected glycals in the presence of 5mM sulfuric acid (Scheme 1).4
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^☆: Presented at the 42e Congrès, A.C.F.A.S., Quebec, Canada, May 1974.

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Catalysis by mercuric ion of reactions of glycals with water☆

Abstract

Advan. Carbohydr. Chem.

Advan. Carbohydr. Chem.

Advan. Carbohydr. Chem. Biochem.

Carbohydr. Res.

J. Biol. Chem.

Advan. Carbohydr. Chem.

Ber.

Methods Carbohydr. Chem.