Extending the scope of the Ferrier reaction: fragmentation-rearrangement reactions of selectively substituted 1,2-cyclopropanated glucose derivatives

Extending the scope of the Ferrier reaction: fragmentation-rearrangement reactions of selectively substituted 1,2-cyclopropanated glucose derivatives

[Display omitted] ► 1,2-Cyclopropanated glucose bearing an ester is unreactive with Lewis acids. ► Reduction and acetylation gives the corresponding cyclopropylcarbinyl acetate. ► This undergoes facile Ferrier-type rearrangement to give 2-C-vinyl glucosides. ► Analogous secondary acetates formed fro...

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Bibliographic Details
Published in:Carbohydrate research Vol. 351; pp. 49 - 55
Main Authors: Munyololo, Muganza, Gammon, David W., Mohrholz, Ilka
Format: Journal Article
Language:English
Published: Netherlands Elsevier Ltd 01-04-2012
Subjects:
acetic acid
aluminum
carbon
Cyclopropanated sugars
Cyclopropanes - chemistry
Ferrier reaction
glucose
Glucose - chemistry
glucosides
Glycals
Lewis acids
Stereoisomerism
Substrate Specificity
Glycals
Cyclopropanated sugars
Ferrier reaction
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Summary:[Display omitted] ► 1,2-Cyclopropanated glucose bearing an ester is unreactive with Lewis acids. ► Reduction and acetylation gives the corresponding cyclopropylcarbinyl acetate. ► This undergoes facile Ferrier-type rearrangement to give 2-C-vinyl glucosides. ► Analogous secondary acetates formed from the ester lead to C-2 alkenylated sugars. ► A novel Ferrier-type rearrangement to unsaturated 2-C-formyl glucose is described. Two further variations of the Ferrier-type allylic rearrangements of 1,2-cyclopropanated glucose derivatives bearing an acetoxylated carbon at the 1′-position are described. In the first, treatment of the cyclopropanated sugar with a nucleophile (ROH, PhSH, azide) and Lewis acid (BF3·Et2O or Al(OTf)3), gives 2-C-vinyl glucosides in good yields and α-selectivities. Alternatively, treatment with a combination of Lewis acid and acetic acid leads to a novel fragmentation-rearrangement to form a 2,3-dehydro-2-formyl-C-glycoside. [Display omitted]
Bibliography:http://dx.doi.org/10.1016/j.carres.2012.01.006
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0008-6215
1873-426X
DOI:10.1016/j.carres.2012.01.006