Access to 2,4-Dien-6-ynoic Acid Esters Using Selenium Chemistry. Formal Synthesis of Z,Z-Dodeca-3,6-dien-1-ol (Trail Pheromone Mimic of the Subterranian Termite Reticulitermes virginicus) and Z,Z-Dodeca-3,6-dien-11-olide (Aggregation Pheromone of the Grain Beetles Oryzaephilus mercartor and O. surinamensis)

Abstract

Esters of 2,4-dien-6-ynoic acids were prepared from terminal acetylenes by lithiation, 1,2-addition to acrolein, orthoester Claisen–Johnson rearrangement and α-(4-methoxyphenyl)selenation/oxidative elimination to introduce the α,β-unsaturation.