Carbanionic Reactivity of the Anomeric Center in Carbohydrates

Somsák, László

doi:10.1021/cr980007n

Cited by 153 publications

(61 citation statements)

References 347 publications

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“…Prior work in the synthesis of anomeric nucleophiles has illuminated some of the critical problems associated with placing am etal at the anomeric carbon. [10] For instance,C 1o rganolithium reagents are widely used and are often accessible in high anomericp urity.H owever,t heir configurational stability is compromised when temperatures rise above À50 8Cl eadingt ot he formation of the thermodynamic product (e.g.,the b anomer in the case of d-glucose and d-galactose). [11] Such instability renders these reagents impractical for use in the stereoretentive glycosyl cross-couplingr eaction.…”

Section: Synthesis Of Anomeric Stannanesmentioning

confidence: 99%

Rethinking Carbohydrate Synthesis: Stereoretentive Reactions of Anomeric Stannanes

Zhu

O’Neill

Rodriguez

et al. 2018

Chemistry A European J

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In this Concept article, we highlight recent advances in the synthesis and applications of anomeric nucleophiles, a class of carbohydrates in which the C1 carbon bears a carbon-metal bond. First, we discuss the advantages of exploiting the carboanionic reactivity of carbohydrates and the methods for the synthesis of mono- and oligosaccharide stannanes. Second, we discuss recent developments in the glycosyl cross-coupling method resulting in transfer of anomeric configuration from C1 stannanes to C-aryl glycosides. These highly stereoretentive processes are ideally suited for the preparation of and was demonstrated in the synthesis of antidiabetic drugs. Next, we highlight the applications of glycosyl cross-coupling method to the preparation of Se-glycosides and in glycodiversification of small molecules and peptides. These reactions proceed with exclusive anomeric control for a broad range of substrates and tolerate carbohydrates with free hydroxyl groups. Taken together, anomeric nucleophiles have emerged as powerful tools for the synthesis of oligosaccharides and glycoconjugates and their future applications will open new avenues to incorporate saccharides into small molecules and biologics.

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Section: Synthesis Of Anomeric Stannanesmentioning

confidence: 99%

Rethinking Carbohydrate Synthesis: Stereoretentive Reactions of Anomeric Stannanes

Zhu

O’Neill

Rodriguez

et al. 2018

Chemistry A European J

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show abstract

“…The addition of carbanions to anomeric electrophiles: 423 There is a plethora of methods for the addition of a carbanion to an anomeric electrophile, and only a few will be mentioned here. The substitution by a nucleophilic reagent of a glycosyl halide is one of the older methods, but yields are often low, especially with ester protecting groups in the sugar:…”

Section: C-glycosides 408-419mentioning

confidence: 99%

Formation of the Glycosidic Linkage

Williams¹

2009

Carbohydrates: The Essential Molecules of Life

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“…[7] Many synthetic approaches for the preparation of glycals have been devised. [8] The original Fischer-Zach method, [9] which uses zinc dust in acetic acid in the reductive elimination of acylated glycosyl bromides, has been one of the most popular methods for synthesizing glycals (Scheme 1a). It has been suggested that heterolytic cleavage of the carbon-halogen bond occurs under these acidic conditions, initially to give an anomeric carbocation that, after taking two electrons from the zinc atom, generates a transient carbanion that evolves through the splitting off of an acetate anion.…”

Section: Introductionmentioning

confidence: 99%