Abstract Alkylation or silylation of lithiated Z-1-methoxy-1-buten-3-yne affords the corresponding substituted methoxyenynes which, upon sequential treatment with lithium diisopropylamide followed by chlorotrialkylsilanes, furnish 1-trialkylsilyl-1, 3-diynes and 1, 4- bis-silyl-1, 3-butadiynes, respectively.