Hetero-bis-metalated 1,3,5-hexatrienes are employed in the linchpin coupling of synthetic fragments for the convergent construction of the central pentaene of the antifungal agent 2'-O-methylmyxalamide D and its (6E) isomer. Sequential Stille and Suzuki-Miyaura couplings interpolate the boron/tin triene into the pentaene chain. The total synthesis of O-methylmyxalamide D and its (6E) isomer was accomplished efficiently.