An iron-catalyzed enantioselective and diastereoselective intramolecular olefin aminochlorination reaction is reported (ee up to 92%, dr up to 15 : 1). In this reaction, a functionalized hydroxylamine and chloride ion are utilized as nitrogen and chlorine sources, respectively. This new method tolerates a range of synthetically valuable internal olefins that are all incompatible with existing asymmetric olefin aminochlorination methods.
Based on a preactivation protocol with (p-Tol)2SO/Tf2O, a practical, straightforward, and high-yielding synthesis of α-sialyl C-glycosides was accomplished by coupling N-acetyl-5-N,4-O-oxazolidione protected thiosialoside with various trimethylsilyl enol ethers and allyltrimethylsilanes. High yields and excellent α-selectivities were obtained for the strong π-nucleophiles with large nucleophilicity values (N = 4.4-9.0), irrespective of whether silyl enol ethers, silyl ketene acetals or allyltrimethylsilanes were used for the electrophilic C-sialylation.
A sugar epitope, α-(2,9)-trisialic acid, was synthesized and labeled by cyanine dyes through Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The cyanine tagged oligosialic acid can be utilized as an efficient fluorescent probe to image the glycan-binding receptors on PC-12 cells. The distribution of Sia-binding immunoglobulin-like lectins (Siglecs) for α-(2,9)-trisialic acid was visualized by Cy3/Cy5 or FRET channel fluorescence imaging.
Sweet as sugar: Sialyl sulfoxide protected by N-acetyl-5-N,4-O-oxazolidinone was readily prepared, and its coupling to various sugar acceptors was investigated. When the reaction was promoted by Tf(2)O/(Tol)(2)SO, efficient and highly α-selective sialylation yielded α(2,6), α(2,3), and α(2,4) glycosidic linkages between sialic acid and glucose/glacotose.
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