In contrast to classically protected ω-hydroxy alkynes, ω-terbutoxy alkynes undergo smooth hydroalumination with DIBAL-H. The obtained E or Z alkenyl alanes are iodinated leading to E or Z alkenyl iodides. The ω-terbutoxy group is easily converted into an acetate. The latter compounds are useful synthons for the synthesis of insect pheromones as examplified with two cases.