Conformationally constrained fused bicyclic iminosugars: synthetic challenges and opportunities

Hensienne, Raphaël; Hazelard, Damien; Compain, Philippe

doi:10.24820/ark.5550190.p010.872

Cited by 9 publications

(1 citation statement)

References 90 publications

(156 reference statements)

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“…In parallel with our studies on multivalency, we have continued to enjoy designing ‘small’ molecules with a focus on conformationally constrained glycomimetics. 103 104 Our studies have aimed at exploring unfrequented regions of glycochemical space, while giving the opportunity to address new synthetic challenges. Constraining a given structure in orientations that fit the binding site of the biological target is a popular strategy in drug discovery.…”

Section: Sweet Curiositiesmentioning

confidence: 99%

From Sweet Molecular Giants to Square Sugars and Vice Versa

Compain¹

2023

Synlett

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This account describes our recent studies in the field of glycomimetics. Our efforts in understanding the structural basis of multivalent effects in glycosidase inhibition have led to decisive mechanistic insights supported by X-ray diffraction analyses and to the discovery of multimeric iminosugars displaying one of the largest binding enhancements reported so far for a non-polymeric enzyme inhibitor. Pushing the limits of the inhibitory multivalent effect has also driven progress in synthetic methodology. The unexpected observation of side products en route to the synthesis of our targets has been the starting point of several new synthetic methodologies, including metal-free deoxygenation of alcohols and one-pot double thioglycosylation. In parallel to our work on ‘giant’ neoglycoclusters, we have developed access to original constrained glycomimetics based on a 4-membered ring (‘square sugars’). Carbohydrates with a quaternary (pseudo)anomeric position were also synthesized from exo-glycals through catalytic hydrogen atom transfer and a novel oxidative radical-polar crossover process.1 Introduction2 Sweet Giants3 Multivalency Spin-Offs4 Sweet Curiosities4.1 Square Sugars4.2 From C,C-Glycosides to Formal Glycosylation of Quinones5 Conclusion

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Section: Sweet Curiositiesmentioning

confidence: 99%

From Sweet Molecular Giants to Square Sugars and Vice Versa

Compain¹

2023

Synlett

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Stereospecific Synthesis of Glycoside Mimics Through Migita‐Kosugi‐Stille Cross‐Coupling Reactions of Chemically and Configurationally Stable 1‐C‐Tributylstannyl Iminosugars

Jaszczyk

Pannecoucke

et al. 2020

Adv Synth Catal

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A process for the de novo synthesis of imino‐C‐glycosides is described. The methodology is based on the reaction of 1‐C‐stannylated iminosugars with various electrophiles under the conditions of Migita‐Kosugi‐Stille cross‐couplings, which gives 1‐C‐substituted iminosugar derivatives in a stereoretentive process. The required iminoglycosyl stannanes are obtained by way of the highly stereoselective addition of tributylstannyllithium to (SR)‐ or (SS)‐N‐tert‐butanesulfinyl glycosylamines, followed by an activation cyclization sequence. Most interestingly, the methodology is tunable: the configuration of the tin adduct is controlled exclusively by the tert‐butanesulfinyl auxiliary, thus giving access after ring formation to ‘α’‐configured or ‘β’‐configured iminoglycosyl stannanes. With the subsequent stereoretentive C−C bond‐forming process, the methodology allows the synthesis of pseudo anomers of imino‐C‐glycosyl compounds in a controlled fashion.

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Conformationally Restricted Oxazolidin‐2‐one Fused Bicyclic Iminosugars as Potential Glycosidase Inhibitors

et al. 2020

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Conformationally constrained fused bicyclic iminosugars: synthetic challenges and opportunities

Abstract: Dedicated to Prof. Stephen Hanessian in recognition of his incomparable achievements in the field of organic chemistry on the occasion of his 84 th anniversary

Cited by 9 publications

References 90 publications

From Sweet Molecular Giants to Square Sugars and Vice Versa

From Sweet Molecular Giants to Square Sugars and Vice Versa

Stereospecific Synthesis of Glycoside Mimics Through Migita‐Kosugi‐Stille Cross‐Coupling Reactions of Chemically and Configurationally Stable 1‐C‐Tributylstannyl Iminosugars

Conformationally Restricted Oxazolidin‐2‐one Fused Bicyclic Iminosugars as Potential Glycosidase Inhibitors

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