Synthesis of 2‐Deoxy Sugars

Giese, Bernd; Gröninger, Kay S.; Witzel, T.; Korth, Hans‐Gert; Sustmann, Reiner

doi:10.1002/anie.198702331

Cited by 63 publications

(21 citation statements)

References 10 publications

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“…59,60 The surprising feature of this reaction is the fact that it proceeds toward the less electronically stabilized radical. Giese has suggested that the anomeric stabilization attained by placing the ester at the 1-position likely outweighs the loss of stabilization of the actual radical center.…”

Section: Estersmentioning

confidence: 96%

Chemistry of β-(Acyloxy)alkyl and β-(Phosphatoxy)alkyl Radicals and Related Species: Radical and Radical Ionic Migrations and Fragmentations of Carbon−Oxygen Bonds

et al. 1997

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ContentsI. Introduction 3273 II. Rearrangements 3275 A. β-(Acyloxy)alkyl Rearrangement 3275 1. Esters 3275 2. Lactones 3280 3. Thiocarbonyl Esters 3280 B. β-(Phosphatoxy)alkyl Rearrangement 3282 C. β-(Nitroxy)alkyl and β-(Sulfonatoxy)alkyl Rearrangements 3285 D. (Acyloxyalkyl)silyl Radical Rearrangement 3285 III. Fragmentation Reactions 3286 A. β-(Acyloxy)alkyl Radicals and Their Thiocarbonyl Analogues 3286 B. β-(Phosphatoxy)alkyl Radicals 3288 1. Anaerobic Conditions 3288 2. Aerobic Conditions 3293 C. β-(Sulfonatoxy)alkyl and Related Radicals 3294 IV. Mechanism 3294 A. β-(Ester)alkyl Radicals Susceptible to Neither Rearrangement Nor Fragmentation 3294 B. Fragmentation Reactions 3295 C. Rearrangement Reactions 3295 1. Noncage Dissociative Pathways 3296 2. Stepwise Pathways via Five-Membered Cyclic Intermediate Radicals 3296 3. Use of Isotopic and Stereochemical Labeling as Probes of Mechanism 3296 4. Quantitative Structure Activity Relationships 3298 5. Computational Studies and ESR Considerations 3299 V. Overview of β-(Ester)alkyl Radical Reactions 3303 VI. Related Reactions Involving Radical C−O Bond Shift and Cleavage 3305 A. Rearrangement and Fragmentation of β-Hydroxyalkyl Radicals 3305 B. Schenck or Allylperoxy Radical Rearrangement 3307 C. β-(Vinyloxy)alkyl to 4-Ketobutyl Rearrangement 3308 VII. Acknowledgments 3309 VIII. References 3309 Scheme 6

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Section: Estersmentioning

confidence: 96%

Chemistry of β-(Acyloxy)alkyl and β-(Phosphatoxy)alkyl Radicals and Related Species: Radical and Radical Ionic Migrations and Fragmentations of Carbon−Oxygen Bonds

et al. 1997

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“…Giese was the first to expand this 1,2-migration to carbohydrates, observing that, starting from acetylated models, such as 21, or benzoylated glycopyranosyl, or furanosyl halides or selenides, 2-deoxy sugars 172 were obtained in good yields by a cisselective rearrangement (Scheme 24). 211,212 It was also demonstrated that the slow addition of nBu 3 SnH required to avoid the direct reduction of the starting substrate may be circumvented by the use of alternative reductants such as TTMSS. 213 A further alternative to tin hydrides was proposed by Quiclet-Sire and Zard, 214 using S -glycosyl xanthates, such as 173, as radical precursors in refluxing cyclohexane, which surprisingly acts as an effective hydrogen donor, and dilauroyl peroxide (DLP) as initiator to give 2-deoxy carbohydrates 174 in good yields.…”

Section: Synthesis Of 2-deoxy Sugars By Radical-induced 12-ester Rear...mentioning

confidence: 99%

Radicals and Carbohydrates

Pérez‐Martín

Suárez

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

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“…For α-linked C -glycosides, stereoselective synthesis can often be achieved through the use of a glycosyl radical, as first described by Giese. 7 8 In the case of β-linked C -alkyl glycosides synthesis often commences with the construction of C -acyl or homoacyl glycosides. This is typically achieved through addition to lactones followed by reduction, 9 cross-coupling of anomeric stannanes, 10 or direct displacement of a leaving group.…”

Section: Introductionmentioning

confidence: 99%

Evolution of a Reagent-Controlled Strategy for β-Selective C-Glycoside Synthesis

Bennett

2022

Synlett

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C-alkyl glycosides represent an attractive class of non-hydrolyzable carbohydrate mimetics which possess enormous potential as next-generation therapeutics. Methods for the direct stereoselective synthesis of C-alkyl glycosides with a broad substrate tolerance are limited, however. This is especially in the case of β-linked C-alkyl glycosides, where direct methods for synthesis from commonly available coupling partners remain limited. This account describes the evolution of our laboratory’s studies on glycosyl sulfonate chemistry from a method for the construction of simple β-linked 2-deoxy-sugars to a technology for the direct synthesis of β-linked acyl and homoacyl glycosides that can be elaborated into more complex structures.

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Synthesis of 2‐Deoxy Sugars

Cited by 63 publications

References 10 publications

Chemistry of β-(Acyloxy)alkyl and β-(Phosphatoxy)alkyl Radicals and Related Species: Radical and Radical Ionic Migrations and Fragmentations of Carbon−Oxygen Bonds

Chemistry of β-(Acyloxy)alkyl and β-(Phosphatoxy)alkyl Radicals and Related Species: Radical and Radical Ionic Migrations and Fragmentations of Carbon−Oxygen Bonds

Radicals and Carbohydrates

Evolution of a Reagent-Controlled Strategy for β-Selective C-Glycoside Synthesis

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