Total and formal syntheses of fostriecin

Two formal syntheses and one total synthesis of fostriecin ( 1 ) have been achieved, as well as, the synthesis of its related congener dihydro-dephospho-fostriecin. All the routes use the Sharpless dihydroxylation to set the absolute stereochemistry at C -8/9 positions and a Leighton allylation to set the C -5 position of the natural product. In the formal syntheses a Noyori transfer hydrogenation of an ynone was used to set the C -11 position while the total synthesis employed a combination of asymmetric dihydroxylation and Pd-π-allyl reduction to set the C -11 position. Finally in the total synthesis, a trans-hydroboration of the C -12/13 alkyne was used in combination with a Suzuki cross coupling to establish the Z , Z , E -triene of fostriecin ( 1 ).