ChemInform Abstract: Thiyl‐Radical Reactions in Carbohydrate Chemistry: From Thiosugars to Glycoconjugate Synthesis

McSweeney, Lauren; Dénès, Fabrice; Scanlan, Eoin M.

doi:10.1002/chin.201625250

Cited by 4 publications

(6 citation statements)

References 1 publication

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“…Contrary to what was observed during the cyclisation of trichloroacetals under atom transfer conditions [ 20 ], and despite the fact that the reaction was carried out at low temperature, the aluminium thioacetal subsequently collapses through a homolytic β-fragmentation pathway to generate an aluminium enolate and a thiyl radical, both of which may remain coordinated to the aluminium. The electron-rich alkene thus generated reacts with the electrophilic thiyl radical to give the thiol-ene addition product [ 22 , 23 ]. Hydrogen atom abstraction followed by aqueous work-up furnishes alcohol 7 .…”

Section: Resultsmentioning

confidence: 99%

Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis

2018

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Thiolactones have attracted considerable attention in recent years as bioactive natural products, lead compounds for drug discovery, molecular probes, and reagents for polymerisation. We have investigated radical-mediated C-C bond forming reactions as a strategy for thiolactone synthesis. Cyclisation of an α-bromo aluminium thioacetal was investigated under radical conditions. It was found that at low temperature, a radical fragmentation and rearrangement process occurs. A putative reaction mechanism involving a previously unreported aluminium templated thiol-ene step for the rearrangement process is presented. Cyclisation reactions of α-bromo thioesters and α-xanthate thioesters under radical mediated conditions furnished the desired thiolactones in moderate yields.

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Section: Resultsmentioning

confidence: 99%

Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis

2018

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“…Thiyl‐radical addition reactions have recently seen increased use in the field of glycoscience . For instance, Borbás and co‐workers have utilized the thiol‐ene reaction for synthesis of thioglycosides and thioether containing sugar derivatives from glycals .…”

Section: Thiol‐ene Cyclization For the Synthesis Of Thiosugarsmentioning

confidence: 99%

“…Thiyl-radical addition reactions have recently seen increased use in the field of glycoscience. [54] For instance, Borbás and co-workers have utilized the thiol-ene reaction for synthesis of thioglycosides and thioether containing sugar derivatives from glycals. [55 -58] Furthermore, advances have been made towards the synthesis of thiosugars through thiylradical additions.…”

Section: Thiol-ene Cyclization For the Synthesis Of Thiosugarsmentioning

confidence: 99%

5‐exo versus 6‐endo Thiyl‐Radical Cyclizations in Organic Synthesis

McCourt

Scanlan

2019

Helvetica Chimica Acta

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Since the discovery of the radical mediated thiol‐ene and thiol‐yne reactions, these reactions have been employed in an intramolecular manner for the synthesis of sulfur‐containing heterocycles. Although closely related on a mechanistic basis, the thiol‐ene and thiol‐yne cyclization can differ greatly in regioselectivity and product distribution, with the thiol‐ene process being more predictable and thus attracting greater utilization. Herein, we review intramolecular thiyl‐radical addition reactions and the factors leading to the observed regioselectivity in examples in which both the 5‐exo and 6‐endo mode of cyclization are feasible. We highlight the applications of these important reactions for organic synthesis in the recent literature.

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“…Finally, thiol-yne coupling (TYC) or thiol-ene coupling (TEC) are mild and high-yielding reactions which proved especially useful in glycosidation synthesis and this topic has recently been reviewed [ 64 ].…”

Section: Functionalized Carbohydrate Scaffoldsmentioning

confidence: 99%

Recent Advances in the Chemistry of Glycoconjugate Amphiphiles

2018

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Glyconanoparticles essentially result from the (covalent or noncovalent) association of nanometer-scale objects with carbohydrates. Such glyconanoparticles can take many different forms and this mini review will focus only on soft materials (colloids, liposomes, gels etc.) with a special emphasis on glycolipid-derived nanomaterials and the chemistry involved for their synthesis. Also this contribution presents Low Molecular Weight Gels (LMWGs) stabilized by glycoconjugate amphiphiles. Such soft materials are likely to be of interest for different biomedical applications.

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ChemInform Abstract: Thiyl‐Radical Reactions in Carbohydrate Chemistry: From Thiosugars to Glycoconjugate Synthesis

Abstract: Review: [68 refs.

Cited by 4 publications

References 1 publication

Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis

Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis

5‐exo versus 6‐endo Thiyl‐Radical Cyclizations in Organic Synthesis

Recent Advances in the Chemistry of Glycoconjugate Amphiphiles

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