ChemInform Abstract: Preparation and Transmetallation of a Triphenylstannyl β‐D‐ Glucopyranoside: Highly Stereoselective Route to β‐D‐C‐Glycosides via Glycosyl Dianions.

Frey, Oliver; Hoffmann, Matthias; Wittmann, Valentin; Kessler, H.; Uhlmann, Peter; Vasella, A.

doi:10.1002/chin.199514254

Cited by 1 publication

(1 citation statement)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…11,29 These indirect protocols are plagued by a competitive glycal formation. 29 Other methods toward C-acyl glycosides involve benzothiazole manipulations, 30 vinylation and oxidative cleavage of the olefins, 31 hydroacylation of glycals, 32 and reactions involving C1 organolithium intermediates 33,34 but require additional synthetic steps to afford glycosyl ketones. Despite these recent advancements, the absence of a general and predictable method for stereospecific anomeric acylation remains a major methodological gap preventing greater investigation into the biology and applications of these compounds as viable precursors to C(sp 3 ) glycomimetics.…”

Section: ■ Introductionmentioning

confidence: 99%

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics

et al. 2018

View full text Add to dashboard Cite

Replacement of a glycosidic bond with hydrolytically stable C–C surrogates is an efficient strategy to access glycomimetics with improved physicochemical and pharmacological properties. We describe here a stereoretentive cross-coupling reaction of glycosyl stannanes with C(sp2)- and C(sp3)-thio(seleno)esters suitable for the preparation C-acyl glycosides as synthetic building blocks to obtain C(sp3)-linked and fluorinated glycomimetics. First, we identified a set of standardized conditions employing a Pd(0) precatalyst, CuCl additive, and phosphite ligand that provided access to C-acyl glycosides without deterioration of anomeric integrity and decarbonylation of the acyl donors (>40 examples). Second, we demonstrated that C(sp3)-glycomimetics could be introduced into the anomeric position via a direct conversion of C1 ketones. Specifically, the conversion of the carbonyl group into a CF2 mimetic is an appealing method to access valuable fluorinated analogues. We also illustrate that the introduction of other carbonyl-based groups into the C1 position of mono- and oligosaccharides can be accomplished using the corresponding acyl donors. This protocol is amenable to late-stage glycodiversification and programmed mutation of the C–O bond into hydrolytically stable C–C bonds. Taken together, stereoretentive anomeric acylation represents a convenient method to prepare a diverse set of glycan mimetics with minimal synthetic manipulations and with absolute control of anomeric configuration.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics

et al. 2018

View full text Add to dashboard Cite

show abstract

ChemInform Abstract: Preparation and Transmetallation of a Triphenylstannyl β‐D‐ Glucopyranoside: Highly Stereoselective Route to β‐D‐C‐Glycosides via Glycosyl Dianions.

Cited by 1 publication

References 1 publication

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics

Contact Info

Product

Resources

About

ChemInform Abstract: Preparation and Transmetallation of a Triphenylstannyl β‐D‐ Glucopyranoside: Highly Stereoselective Route to β‐D‐C‐Glycosides via Glycosyl Dianions.

Cited by 1 publication

References 1 publication

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp3)-Linked Glycomimetics

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp3)-Linked Glycomimetics

Contact Info

Product

Resources

About

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp³)-Linked Glycomimetics