Synthetic Study toward Saccharomicin Based upon Asymmetric Metal Catalysis

Here,
we report a de novo metal-catalyzed approach
toward the stereoselective glycosidic bond formation in saccharomicin.
The signature step is highlighted by the Pd-catalyzed asymmetric coupling
of ene-alkoxyallenes and highly functionalized alcohol substrates.
The reaction showed high chemo-, regio-, and ligand-driven diastereoselectivity.
In combination with the ring-closing metathesis and late-stage functionalization,
this method led to highly efficient synthesis of saccharosamine–rhamnose
and rhamnose–fucose fragments.