Advances in the Synthesis of <i>C</i>-Glycosides from Glycals

Guo, Zhenyan; Bai, Jinhe; Liu, Miao; Xiong, De‐Cai; Ye, Xin‐Shan

doi:10.6023/cjoc202006005

Cited by 18 publications

(8 citation statements)

References 39 publications

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“…These include products with functionalizable C(sp 2 )À Cl bonds (8, 9) as well as heteroarenes (12)(13)(14). Cyclic and acyclic alkenyl motifs could also be incorporated, affording the corresponding stereodefined C-alkenyl glycosides (15,16).…”

Section: Resultsmentioning

confidence: 99%

“…Given the significant biological and medicinal value of C ‐aryl glycosides, developing synthetic methodologies that provide efficient access to these entities with high diastereoselectivity is a compelling objective in carbohydrate research [3, 14–18] . Particularly desirable is a set of broadly applicable protocols that harness the power of nonprecious base metal catalysis [3, 18, 19] to transform a readily available glycosyl precursor (donor), the saccharide component which bears a reactive functional group at the C1 position, into the C ‐aryl glycoside product by controlling the stereochemical outcome of C‐aryl bond formation [18] .…”

Section: Introductionmentioning

confidence: 99%

“…[3,6] Given the significant biological and medicinal value of C-aryl glycosides, developing synthetic methodologies that provide efficient access to these entities with high diastereoselectivity is a compelling objective in carbohydrate research. [3,[14][15][16][17][18] Particularly desirable is a set of broadly applicable protocols that harness the power of nonprecious base metal catalysis [3,18,19] to transform a readily available glycosyl precursor (donor), the saccharide component which bears a reactive functional group at the C1 position, into the C-aryl glycoside product by controlling the stereochemical outcome of C-aryl bond formation. [18] In this regard, processes that convert glycosyl donors into glycosyl radical intermediates [16,17,[20][21][22][23] en route to C-aryl glycosides are highly attractive (Scheme 1b), given that such glycosyl radical cross-coupling reactions are less susceptible to undesired epimerization and elimination side reactions.…”

Section: Introductionmentioning

confidence: 99%

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StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

et al. 2023

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Stereoselective C‐glycosylation reactions are increasingly gaining attention in carbohydrate chemistry because they enable glycosyl precursors, readily accessible as anomeric mixtures, to converge to a single diastereomeric product. However, controlling the stereochemical outcome through transition‐metal catalysis remains challenging, and methods that leverage bench‐stable heteroaryl glycosyl sulfone donors to facilitate glycosylation are rare. Herein, we show two complementary nonprecious metal catalytic systems, based on iron or nickel, which are capable of promoting efficient C−C coupling between heteroaryl glycosyl sulfones and aromatic nucleophiles or electrophiles through distinct mechanisms and modes of activation. Diverse C‐aryl glycosides were secured with excellent selectivity, scope, and functional‐group compatibility, and reliable access to both α and β isomers was possible for key sugar residues.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

et al. 2023

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“…Among carbohydrate-containing natural products or drug candidates, 2-deoxy- C -glycosides are unique structural elements that have attracted considerable interest in carbohydrate chemistry and biochemistry. − Although more challenges in stereoselective routes to 2-deoxy- C -glycosides exist because of the nonexistence of participating groups at the C2-position and inherent susceptibility toward hydrolysis, extensive research efforts have been devoted to expanding the scope of synthetic methods. − From a design perspective, catalytic anomerization would be an efficient procedure for the direct stereochemical editing of 2-deoxy- C -glycosides; however, few examples of C -glycoside anomerization are known to date, notably, the one that proceeds through the endocyclic C1–O5 bond cleavage catalyzed by HBF 4 (Scheme a) . Hence, it is of great interest to exploit new strategies to access the anomerization of 2-deoxy- C -glycosides.…”

Section: Introductionmentioning

confidence: 99%

Reversible-Hydrogen-Transfer-Mediated Anomerization of Azaheterocyclyl 2-Deoxy-C-glycosides and Mechanistic Studies

Guo

Cai

et al. 2023

ACS Catal.

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Mutarotation of O-glycans and O-glycosides has long been well-established and exploited in the stereocontrolled chemical synthesis of O-glycosides, while few examples of C-glycoside anomerization are known to date. During the development of a simple iridium catalyst-promoted α-stereoselective C-glycosylation of 2-indoly-pyridine with glycal donors, we serendipitously discovered the occurrence of 2-deoxy-C-glycoside anomerization, enabling α-to-β configuration conversion. Control experiments and density functional theory calculations were performed to explore the mechanistic details of the anomerization of the C-glycosylation products, which could tolerate C-aryl and C-alkyl-glycosides. The anomerization reaction plausibly proceeds through the pathway involving the activation of the C(sp3)–H bond mediated by the iridium catalyst and reversible hydrogen transfer, rather than the classical anomerization mechanisms involving the endocyclic cleavage of the C1–O5 bond or exocyclic cleavage of the glycosidic bond.

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“…48 Meanwhile, in 2020, Ye et al reviewed the synthesis of C-glycosides from glycals achieved prior to 2010. 49 The present short review aims to…”

Section: Introductionmentioning

confidence: 99%

Recent Advances on the Synthesis of C-Glycosides from 1,2-Glycals

Mukherjee,

Kundu,

Das

et al. 2023

Synthesis

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The development of stereoselective synthetic routes for C-glycosides has attracted immense attention from carbohydrate chemists in the last two decades. In this review, progress made in the last decade towards the synthesis of C-glycosides using glycals as a precursor are discussed. Glycals have been extensively manipulated to generate oxocarbenium cation or glycosyl anion to form C-C bond at the anomeric position through attack with C-nucleophiles or transition metal catalyzed coupling reactions. Recent reports on carbon Ferrier, intramolecular Cope, Claisen rearrangements, various coupling reactions in the presence or absence of directing groups are deliberated herein. Contemporary applications of these reactions in the syntheses of natural products, drugs and scaffolds with bioactive potential are briefly discussed.

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Advances in the Synthesis of C-Glycosides from Glycals

Cited by 18 publications

References 39 publications

StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

Reversible-Hydrogen-Transfer-Mediated Anomerization of Azaheterocyclyl 2-Deoxy-C-glycosides and Mechanistic Studies

Recent Advances on the Synthesis of C-Glycosides from 1,2-Glycals

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