Direct synthesis of unprotected aryl C-glycosides by photoredox Ni-catalysed cross-coupling

Zhang, Chen; Xu, Shuo; Zuo, Hao; Zhang, Xia; Dang, Qiu-Di; Niu, Dawen

doi:10.1038/s44160-022-00214-1

Cited by 68 publications

(39 citation statements)

References 77 publications

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“…[47] Following stereoretentive reductive elimination, V is secured in high β (1,2trans) selectivity. [49] Overall, the stereochemical outcomes observed in Tables 1 and 2 could be reasonably rationalized by these mechanistic deliberations.…”

Section: Forschungsartikelmentioning

confidence: 74%

“…In this case, attack from the opposite face (to form IV ) would risk severe steric clash with the C2 alkoxy, which is exacerbated by the shorter C1−Ni bond (vs. C1−Fe bond) [47] . Following stereoretentive reductive elimination, V is secured in high β (1,2‐ trans ) selectivity [49] . Overall, the stereochemical outcomes observed in Tables 1 and 2 could be reasonably rationalized by these mechanistic deliberations.…”

Section: Resultsmentioning

confidence: 91%

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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: Forschungsartikelmentioning

confidence: 74%

Section: Resultsmentioning

confidence: 91%

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

et al. 2023

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“…Although several novel glycosyl donors have successfully participated in synthesizing C-glycosides, such as glycosyl esters, [15,28,34] and allyl glycosyl sulfones. [20] Further efforts are still needed to exploit their potential in glycosylation.…”

Section: Discussionmentioning

confidence: 99%

“…The same group reported a direct synthesis of unprotected aryl C-glycosides by photoredox/nickel-catalyzed cross-coupling of bench-stable allyl glycosyl sulfones with aryl halides (Scheme 9). [20] The developed protocol features a wide scope of aryl halides and allyl glycosyl sulfones, delivering desired products in moderateto-good yields with high 1,2-trans selectivities. A great functional group tolerance was observed in aryl halide coupling partners, though a limitation of scope was observed in the reaction of aryl iodides bearing a bulky, ortho -isopropyl group.…”

Section: Hosted Filementioning

confidence: 99%

C-Glycoside Synthesis Enabled by Nickle Catalysis

Niu

Shang

Shi

2023

Preprint

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C-Glycosides are critical, naturally occurring products and medicinal candidates, and extensive efforts have been made to explore efficient approaches for creating C-glycosidic bonds. Transition-metal-catalysis, particularly nickel-catalyzed C-glycosylation reactions constitute a promising strategy. However, achieving a stereoselective synthesis of α- and β-C-glycosides has been a long-standing challenge. To address this problem, a variety of nickel-mediated strategies have been developed. This review highlights recent developments in the nickel-catalyzed diastereoselective C-glycosylation reactions and briefly summarizes the mechanistic understandings of these methods.

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“…Therefore, it is highly desirable to develop a modular and streamlined synthetic platform for such medicinally relevant glycosides with well-defined anomeric configurations and outstanding control of Z / E geometry. In recent years, chemical glycosylations, particularly, transition-metal catalyzed glycosylations, , have emerged as powerful and practical tools for the synthesis of various glycosides and glycoconjugates owing to their versatility, efficiency, and stereoselectivity. We envision that the mildness of activation with transition metal catalysis might offer a good alternative to synthesize aminooxy glycosides through direct coupling of oximes.…”

mentioning

confidence: 99%

Stereospecific Palladium-Catalyzed Direct Glycosylation of Oximes: Access to N–O-Linked Glycosides

et al. 2023

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A highly efficient, palladium-catalyzed glycosylation between 3,4-O-carbonate glycals and acid-labile oximes is disclosed. This approach features broad substrate scope, high functional group tolerance, and easy scalability, delivering glycosyl oximes in excellent yields with exclusive β-selectivity and retention of Z/E geometries. The power of this method is demonstrated by a set of site-selective transformations of glycosylation products and late-stage glycodiversification of bioactive molecules. Overall, our strategy provides an efficient toolkit for facile access to valuable N–O-linked glycosides.

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Direct synthesis of unprotected aryl C-glycosides by photoredox Ni-catalysed cross-coupling

Cited by 68 publications

References 77 publications

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

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

C-Glycoside Synthesis Enabled by Nickle Catalysis

Stereospecific Palladium-Catalyzed Direct Glycosylation of Oximes: Access to N–O-Linked Glycosides

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