Preparation of propargyl 1,2-orthoesters of carbohydrates: From side reactions in dichloromethane to optimized reaction conditions in acetonitrile

In this note, supercritical fluid chromatography coupled to high-resolution mass spectrometry (SFC-HRMS) has been used to identify a chloro glycoside formed during the preparation of propargyl 1,2-orthoesters in dichloromethane. Additional studies revealed that 20–40% of this side-product was obtained depending on the source of anhydrous solvent, and that tetrabutylammonium iodide amplifies this side-reaction. Finally, a reliable procedure was developed in acetonitrile to prepare these glycosyl donors from perbenzoylated bromo glycosides in manno, gluco and galacto series in 63–74% yield. [Display omitted]