Samarium Diiodide-Mediated Reductive Coupling of Epoxides and Carbonyl Compounds: A Stereocontrolled Synthesis of C-Glycosides from 1,2-Anhydro Sugars

Chiara, José Luis; Sesmilo, Esther

doi:10.1002/1521-3757(20020902)114:17<3376::aid-ange3376>3.0.co;2-l

Cited by 6 publications

(1 citation statement)

References 54 publications

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“…For instance, SmI 2 -promoted reductive coupling of α-glycosyl epoxides with isobutyraldehyde in the presence of NiI 2 gave α-C-glycosides 454 and 455 exclusively through the anomeric radical A, whereas similar reactions with acetone afforded β-C-glycosides 456 and 457 as the major isomers (Scheme 74). 363 In terms of β-epoxide sugars, couplings with both aldehydes and ketones under similar conditions stereoselectively yielded α-C-glycosides.…”

Section: C-glycosylation With 12-anhydro Sugars Through Glycosyl Radi...mentioning

confidence: 99%

Recent Advances in the Chemical Synthesis of C-Glycosides

2017

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Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C-C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg-Bäcklund rearrangement, and 1,2-Wittig rearrangement, which usually involve concerted pathways, constitute another category of C-glycosylations. An alternative to the C-glycosylations is the formation of pyranoside/furanoside rings after construction of the predetermined glycosidic C-C bonds, which might involve cyclization of acyclic precursors or D-A cycloadditions. Throughout, the stereoselectivity in the formation of the resultant C-glycosidic linkages is highlighted.

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Section: C-glycosylation With 12-anhydro Sugars Through Glycosyl Radi...mentioning

confidence: 99%

Recent Advances in the Chemical Synthesis of C-Glycosides

2017

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Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis ofC‐linked Glycoconjugates

Shang

Shi

et al. 2020

Angewandte Chemie

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We here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available,air and moisture stable precursors to glycosyl radicals.These glycosyl sulfoxides could be converted to glycosyl radicals by way of arapid and efficient intramolecular radical substitution event. The use of this type of precursors enabled the synthesis of various complex Clinked glycoconjugates under mild conditions.T his reaction could be performed in aqueous media and is amenable to the synthesis of glycopeptidomimetics and carbohydrate-DNA conjugates. Scheme 1. a) Glycosyl radicals as valuable intermediates in C-glycoside synthesis. b) Our strategy to generate glycosyl radicals.

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Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

Zhang

et al. 2023

Angewandte Chemie

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We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to the success is the design and use of glycosyl sulfinates as radical precursors, which are bench-stable solids and can be readily prepared from commercial starting materials. This development allows the installation of glycosyl units onto pyridine rings directly by the Minisci reaction. We further demonstrate the utility of this method in the late-stage modification of complex drug molecules, including the anticancer agent camptothecin. Experimental studies provide insight into the reaction mechanism.

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Samarium Diiodide-Mediated Reductive Coupling of Epoxides and Carbonyl Compounds: A Stereocontrolled Synthesis of C-Glycosides from 1,2-Anhydro Sugars

Cited by 6 publications

References 54 publications

Recent Advances in the Chemical Synthesis of C-Glycosides

Recent Advances in the Chemical Synthesis of C-Glycosides

Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis ofC‐linked Glycoconjugates

Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

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