Total Synthesis of (2 Z )‐[(4 R ,5 R ,6 S )‐6‐( β ‐ D ‐Glucopyranosyloxy)‐4,5‐dihydroxycyclohex‐2‐en‐1‐ylidene]ethanenitrile, a Cyanoglucoside from Ilex warburgii

The total synthesis of the noncyanogenic cyanoglucoside 1 , originally isolated from Ilex warburgii , was achieved in nine steps (9% overall yield), starting from an optically pure Diels–Alder adduct ((+)‐ 3 ). The key step of the synthesis, the glycosidation, was carried out under Koenigs–Knorr conditions closely related to those developed for the total syntheses of (−)‐lithospermoside and (−)‐bauhinin. We had to tune the protecting groups used for the two free cis ‐configured OH groups of the aglycone, which afforded the desired β ‐ d‐ glucoside intermediate 15 in very good yield (62%).