Alkoxyl migration in displacement of a 5-trifluoromethanesulfonyloxy group from ribofuranosides

Iyer, Vaidyanathan K.; Horwitz, Jerome P.

doi:10.1021/jo00343a008

Cited by 15 publications

(2 citation statements)

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“…Indeed, in the case mentioned previously involving azide displacement of the highly reactive triflate from C-2 of a protected methyl-a-D-mannopyranoside, no evidence was obtained for a migration product, simply a product of an elimination reaction. However, migration has been observed in attempts to perform displacements of the highly reactive triflate leaving group (21), where a methyl ether migration from the anomeric centre to C-5 of a pentopyranosyl5-triflate occurred.…”

Section: Resultsmentioning

confidence: 99%

Fluorination of protected mannose derivatives using diethylaminosulfur trifluoride

Street¹,

Withers²

1986

Can. J. Chem.

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.3,4,6-Tri-0-benzyl-D-mannose and methyl 3,4,6-tri-0-benzyl-a-D-mannopyranoside were subjected to fluorination by diethylaminosulfur trifluoride and each produced two products. The former suffered fluorination at the anomeric centre to give the a-fluoride and, to a lesser extent, additionally at C-2 to give the 2-fluoro-2-deoxy-P-D-glucopyranosyl fluoride. The methyl mannoside underwent a methyl ether migration reaction to produce a 1 : 1 mixture of the a-and P-2-0-methyl glucosyl fluorides.A mechanism for this rearrangement is proposed and 'H and ' % nmr data are presented for all products. [Traduit par la revue]

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Section: Resultsmentioning

confidence: 99%

Fluorination of protected mannose derivatives using diethylaminosulfur trifluoride

Street¹,

Withers²

1986

Can. J. Chem.

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“…Nucleophilic substitution in which the leaving group is replaced by a sulfonatomethyl moiety3 appears to be the most rapid and facile route to the carbohydrate sulfonate esters. However, previous reactions were limited to O ‐glycosides and suffered from a significant disadvantage: reaction of a lithiated methanesulfonate ester with a 6‐iodocarbohydrate gave the corresponding sulfonate in low yield,3,6b whereas with the use of the more reactive carbohydrate‐6‐ O ‐triflate, anchimeric assistance of the anomeric alkoxy group in the displacement of the triflate was observed 6a,11…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 6‐Sulfonatomethyl Thioglycosides by Nucleophilic Substitution: Methods to Prevent 1→6 Anomeric Group Migration of Thioglycoside 6‐O‐Triflates

et al. 2013

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Introduction of a sulfonatomethyl moiety into the primary position of thioglycosides by nucleophilic displacement of the corresponding 6‐O‐triflate is described. The 1→6 migration of the anomeric group, which inevitably occurs through a bicyclic sulfonium ion intermediate, from conformationally flexible β‐thioglycosides was prevented by using an α‐thioglycoside or conformationally locked β‐thioglycoside as the starting material. The thioglycoside 6‐sulfonic acids showed excellent α‐selectivity during synthesis of uronic acid containing heparinoid trisaccharides.

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Protection for the Hydroxyl Group, Including 1,2‐ and 1,3‐Diols

Wuts

Greene²

2006

Greene's Protective Groups in Organic Synthesis

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Alkoxyl migration in displacement of a 5-trifluoromethanesulfonyloxy group from ribofuranosides

Cited by 15 publications

References 0 publications

Fluorination of protected mannose derivatives using diethylaminosulfur trifluoride

Fluorination of protected mannose derivatives using diethylaminosulfur trifluoride

Synthesis of 6‐Sulfonatomethyl Thioglycosides by Nucleophilic Substitution: Methods to Prevent 1→6 Anomeric Group Migration of Thioglycoside 6‐O‐Triflates

Protection for the Hydroxyl Group, Including 1,2‐ and 1,3‐Diols

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