64495-84-7

Upstream product

• 37556-51-7 S-cyclohexyl 4-methylbenzenesulfonothioate 
• 572-09-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 
• 604-69-3 β-D-glucose pentaacetate 
• 1569-69-3 Cyclohexanethiol 
• 3947-62-4 2,3,4,5-tetra-O-acetyl-D-glucopyranose 
• 604-68-2 α-D-glucopyranose peracetylate 
• 13035-49-9 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl iodide 

Downstream Products

• 66108-02-9 1-Cyclohexylthio-β-D-glucose 

Relevant academic research and scientific papers

Anodic Reactivity of Alkyl S-Glucosides

A voltammetric study of a series of alkyl and aryl S-glucosides unveiled the reactivity patterns of alkyl S-glucosides toward anodic oxidation and found noteworthy differences with the trends followed by aryl derivatives. The oxidation potential of alkyl S-glucosides, estimated herein from square-wave voltammetry peak potentials (Ep), depends on the steric properties of the aglycone. Glucosides substituted with bulky groups exhibit Ep values at voltages more positive than the values of those carrying small aglycones. This relationship, observed in all analyzed alkyl series, is evidenced by good linear correlations between Ep and Taft's steric parameters (ES) of the respective alkyl substituents. Moreover, the role of the aglycone's steric properties as a primary reactivity modulator is backed by poor correlations between Ep and the radical stabilization energies (RSEs) of the aglycone-derived thiyl radicals (RS?). In contrast, aryl glucosides' Ep values exhibit excellent correlations with the aryl substituents' Hammett parameters (σ+) and the ArS?RSEs, evidencing the inherent stability of the reactive radical intermediate as the primary factor controlling aryl glucoside's electrochemical reactivity. The reactivity differences between alkyl and aryl S-glucosides also extend to the protective group's effect on Ep. Alkyl S-glucosides' reactivity proved to be more sensitive to protective group exchange.

Synthesis of glycosyl sulfoximines by a highly chemo- And stereoselective NH- And O-transfer to thioglycosides

A synthesis of unprecedented and stable glycosyl sulfoximines is reported. The developed strategies represent the first example of highly stereoselective sulfoximine formation directly from thioglycosides. This synthetic protocol has been tested on severa

Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy

While strategies involving a 2e- transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the development of the radical process has been challenging owing to notorious competing reduction, elimination and/or SN side reactions of commonly used, labile glycosyl donors. Here we introduce an organophotocatalytic strategy through which glycosyl bromides can be efficiently converted into corresponding anomeric radicals by photoredox mediated HAT catalysis without a transition metal or a directing group and achieve highly anomeric selectivity. The power of this platform has been demonstrated by the mild reaction conditions enabling the synthesis of challenging α-1,2-cis-thioglycosides, the tolerance of various functional groups and the broad substrate scope for both common pentoses and hexoses. Furthermore, this general approach is compatible with both sp2 and sp3 sulfur electrophiles and late-stage glycodiversification for a total of 50 substrates probed.

Urea–hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones

A practical method for the selective and controlled oxidation of thioglycosides to corresponding glycosyl sulfoxides and sulfones is reported using urea–hydrogen peroxide (UHP). A wide range of glycosyl sulfoxides are selectively achieved using 1.5 equiv of UHP at 60 °C while corresponding sulfones are achieved using 2.5 equiv of UHP at 80 °C in acetic acid. Remarkably, oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide.

Dehydrative Thioglycosylation of 1-Hydroxyl Glycosides Catalyzed by In Situ-Generated AlI3

Thioglycosylation of 1-hydroxyl glycosides catalyzed by in situ-generated AlI3 from elemental aluminium and molecular iodine has been developed. This method provides an alternative route to access anomeric thioglycosides without the use of hazard Lewis acidic activators or per-modified activated thiol sources. The major advantages of this dehydrative procedure are environmental friendly, ease of operation, high anomeric diastereoselectivity, and mild reaction conditions.

Facile preparation of α-glycosyl iodides by in situ generated aluminum iodide: Straightforward synthesis of thio-, seleno-, and o-glycosides from unprotected reducing sugars

A facile and practical protocol was developed for the synthesis of glycosyl iodides using AlI3 generated in situ from cheap aluminum metal and molecular iodine. Furthermore, in combination with iodine-catalyzed per-O-acetylation, sequential synthesis of per-acetylated glycosyl iodides, per-acetylated thioglycosides, selenoglycoside, and O-glycosides from unprotected reducing sugars was also achieved with complete diastereocontrol in a one-pot version. Supplemental material is available for this article. Go to the publisher's online edition of Journal of Carbohydrate Chemistry to view the free supplemental file. Copyright Taylor & Francis Group, LLC.

Diastereoselective thioglycosylation of peracetylated glycosides catalyzed by in situ generated iron(III) iodide from elemental iodine and iron

A facile in situ preparation of Fe(III) iodide from cheap, abundant elemental iodine and iron metal served as an efficient catalyst for the thioglycosylation of peracetylated glycosides with various alkyl and aryl mercaptans. Due to neighboring participation, the anomerically pure β-thioglycosides were obtained in good to high yields with exclusive diastereocontrol.

Involvement of the S-aglycon in the conformational preferences of thioglucosides

The conformational preferences of two series of alkyl β-d-thioglucopyranosides in solution were investigated by NMR and CD. The rotamer populations of the hydroxymethyl group were found to depend on the structural nature of the S-aglycon. The population of the gt rotamer increased and that of the gg rotamer decreased as the alkyl group attached to the S atom increased in size. These rotamer populations have a linear correlation with the Taft' steric parameters, the nS s(-) σC s(-) O* exo-anomeric interaction may express these rotational preferences. Comparative analysis of the hydroxymethyl populations between alkyl O- and S-glucosides revealed identical or slightly higher gt and smaller gg populations for the latter compounds.

Highly diastereoselective thioglycosylation of functionalized peracetylated glycosides catalyzed by MoO2Cl2

Among 18 oxometallic species, MoO2Cl2 was found to be the most reactive in catalytic thioglycosylation of O-acetylated glycosides with functionalized thiols in CH2Cl2, leading cleanly to 1,2-trans-thioglycosides with exclusive diastereocontrol. The new catalytic protocol is applicable to a monoglycoside building block and β-(1→6)-S-linked-thiodisaccharide synthesis.