Selective Acetylation of Non-anomeric Groups of per-O-Trimethylsilylated Sugars

Selective modification of the hydroxyl groups of sugars has been a long-standing challenge due to their proximate relative reactivity. Herein, we report a TMSOTf-catalyzed selective acetylation of the non-anomeric hydroxyl groups of several per-O-TMS-protected sugar substrates while leaving their anomeric group unaffected. In addition to standing versatile by itself, the anomeric O-TMS group left intact can be functionalized to afford key sugar precursors such as imidate donors, which could otherwise be synthesized via a stepwise anomeric deprotection-functionalization procedure.

Automated summary

This method allows for selective acetylation of the non-anomeric hydroxyl groups of sugars, while leaving the anomeric hydroxyl group unaffected. The intact anomeric O-TMS group can be functionalized to produce important sugar precursors, simplifying the synthesis process.