A 3,4-trans-Fused Cyclic Protecting Group Facilitates α-Selective Catalytic Synthesis of 2-Deoxyglycosides**
نویسندگان
چکیده
A practical approach has been developed to convert glucals and rhamnals into disaccharides or glycoconjugates with high α-selectivity and yields (77-97%) using a trans-fused cyclic 3,4-O-disiloxane protecting group and TsOH⋅H2O (1 mol%) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals because the C6 side-chain conformation augments the selectivity.
منابع مشابه
A 3,4-trans-Fused Cyclic Protecting Group Facilitates a-Selective Catalytic Synthesis of 2-Deoxyglycosides**
A practical approach has been developed to convert glucals and rhamnals into disaccharides or glycoconjugates with high a-selectivity and yields (77–97%) using a trans-fused cyclic 3,4-O-disiloxane protecting group and TsOH·H2O (1 mol%) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals becau...
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The thio-additions of glycals were efficiently promoted by a stoichiometric amount of trimethylsilyl bromide (TMSBr) to produce S-2-deoxyglycosides under solvent-free conditions in good to excellent yields. In addition, with triphenylphosphine oxide as an additive, the TMSBr-mediated direct glycosylations of glycals with a large range of alcohols were highly α-selective.
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