Total Synthesis of Diospyrodin and Its Three Diastereomers.

Antibacterial diospyrodin (1) was synthesized in 13 steps. Et3B and O2 promoted the formation of an α-alkoxy carbon radical from l-ribose-derived α-alkoxyacyl telluride 5, which reacted with d-glucose-derived aldehyde 4. The radical addition realized the convergent assembly of the contiguously hydroxylated carbon-chain of 3-α and greatly contributed to streamlining the synthetic route. Compound 3-α was transformed not only to 1 but also to its three diastereomers by functional group manipulations.