Base‐ and Radical‐Mediated Regio‐ and Stereoselective Additions of Thiols, Thio‐Sugars, and Thiol‐Containing Peptides to Trisubstituted Activated <i>exo</i>‐Glycals

Richard, Mylène; Didierjean, Claude; Chapleur, Yves; Pellegrini‐Moise, Nadia

doi:10.1002/ejoc.201500130

Cited by 8 publications

References 58 publications

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Photoinitiated Thiol−Ene Reactions of Various 2,3‐Unsaturated O‐, C‐ S‐ and N‐Glycosides – Scope and Limitations Study

Kelemen

Csávás

Hotzi

et al. 2020

Chemistry An Asian Journal

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The photoinitiated thiol−ene addition reaction is a highly stereo‐ and regioselective, and environmentally friendly reaction proceeding under mild conditions, hence it is ideally suited for the synthesis of carbohydrate mimetics. A comprehensive study on UV‐light‐induced reactions of 2,3‐unsaturated O‐, C‐, S‐ and N‐glycosides with various thiols was performed. The effect of experimental parameters and structural variations of the alkenes and thiols on the efficacy and regio‐ and stereoselectivity of the reactions was systematically studied and optimized. The type of anomeric heteroatom was found to profoundly affect the reactivity of 2,3‐unsaturated sugars in the thiol−ene couplings. Hydrothiolation of 2,3‐dideoxy O‐glycosyl enosides efficiently produced the axially C2‐S‐substituted addition products with high to complete regioselectivity. Moderate efficacy and varying regio‐ and stereoselectivity were observed with 2,3‐unsaturated N‐glycosides and no addition occurred onto the endocyclic double bond of C‐glycosides. Upon hydrothiolation of 2,3‐unsaturated S‐glycosides, the addition of thiyl radicals was followed by elimination of the thiyl aglycone resulting in 3‐S‐substituted glycals.

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Photoinitiated Thiol−Ene Reactions of Various 2,3‐Unsaturated O‐, C‐ S‐ and N‐Glycosides – Scope and Limitations Study

Kelemen

Csávás

Hotzi

et al. 2020

Chemistry An Asian Journal

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Promotion of a Reaction by Cooling: Stereoselective 1,2‐cis‐α‐Thioglycoconjugation by Thiol‐Ene Coupling at −80 °C

Eszenyi

Kelemen

Balogh

et al. 2018

Chemistry A European J

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The photoinitiated thiol-ene coupling reactions of 2-substituted glycals were studied as a generally applicable strategy for stereoselective 1,2-cis-α-thioconjugation. Although all glycals reacted with full α-selectivity, the efficacy of the reactions varied in a broad range depending on their configuration and glycals bearing axial acetoxy substituents reacted with very low efficacy at room temperature. The study revealed that the reaction progress could be promoted by cooling and inhibited by heating. At -80 °C, the equilibrium of the rapidly reversible addition of the thiyl radical to alkenes is shifted almost completely toward products, leading to efficient addition reactions. By exploiting this unique temperature effect a series of α-thio-l-fucosides, -d-galactosides, and d-GlcNAc derivatives were prepared with high efficacy and complete stereoselectivity.

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ChemInform Abstract: Base‐ and Radical‐Mediated Regio‐ and Stereoselective Additions of Thiols, Thio‐Sugars, and Thiol‐Containing Peptides to Trisubstituted Activated exo‐Glycals.

et al. 2015

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Base-and Radical-Mediated Regio-and Stereoselective Additions of Thiols, Thio--Sugars, and Thiol-Containing Peptides to Trisubstituted Activated exo-Glycals. -The hydrothiolation of the double bond of exo-glycals such as (I) and (IV) is achieved under basic and radical conditions. The basic conditions are generally found to be more efficient. -(RICHARD, M.; DIDIERJEAN, C.; CHAPLEUR, Y.; PELLEGRINI-MOISE*, N.; Eur.

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Base‐ and Radical‐Mediated Regio‐ and Stereoselective Additions of Thiols, Thio‐Sugars, and Thiol‐Containing Peptides to Trisubstituted Activated exo‐Glycals

Cited by 8 publications

References 58 publications

Photoinitiated Thiol−Ene Reactions of Various 2,3‐Unsaturated O‐, C‐ S‐ and N‐Glycosides – Scope and Limitations Study

Photoinitiated Thiol−Ene Reactions of Various 2,3‐Unsaturated O‐, C‐ S‐ and N‐Glycosides – Scope and Limitations Study

Promotion of a Reaction by Cooling: Stereoselective 1,2‐cis‐α‐Thioglycoconjugation by Thiol‐Ene Coupling at −80 °C

ChemInform Abstract: Base‐ and Radical‐Mediated Regio‐ and Stereoselective Additions of Thiols, Thio‐Sugars, and Thiol‐Containing Peptides to Trisubstituted Activated exo‐Glycals.

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