An asymmetric synthesis of the C14-C26 segment of rhizoxin as described in which the three stereogenic centers are derived from a gamma-lactone; stannylcupration-methylation of a terminal alkyne is used to generate an (E)-iodoalkene for Stille coupling with a dienylstannane that produces the conjugated (E,E,E)-triene unit of rhizoxin. (C) 1997 Elsevier Science Ltd.