Abstract(−)‐Pumiliotoxin‐C‐hydrochloride, as well as its unnatural enantiomer, have been synthesized in an enantioselective manner starting from (S)‐ or (R)‐norvaline, respectively. In the crucial cycloaddition step 11 → 12(cf. scheme 2) the chiral center of 11 controls to a major extent the three developing centers of chirality. This synthesis shows unambigously the (2S)‐configuration of natural pumiliotoxin‐C.
Abstract(−)‐Pumiliotoxin‐C‐hydrochloride, as well as its unnatural enantiomer, have been synthesized in an enantioselective manner starting from (S)‐ or (R)‐norvaline, respectively. In the crucial cycloaddition step 11 → 12(cf. scheme 2) the chiral center of 11 controls to a major extent the three developing centers of chirality. This synthesis shows unambigously the (2S)‐configuration of natural pumiliotoxin‐C.