Palladium (0)-catalysed addition of (Me3Sn) 2 to the α, β-acetylenic esters (1a–n) and amides (4a–d) provides the (Z)-2, 3-bis (trimethylstannyl) alk-2-enoates (2a–n) and the (E)- 2, 3-bis (trimethylstannyl) alk-2-enamides (6a–d), respectively; thermolysis of (2a–h) transforms these substances into the corresponding (E)-isomers (3a–h).