STEREOSELECTIVE SYNTHESIS OF 1,4-DIENES - APPLICATION TO THE PREPARATION OF INSECT PHEROMONES (3Z,6Z)-DODECA-3,6-DIEN-1-OL AND (4E,7Z)-TRIDECA-4,7-DIENYL ACETATE

Stereoselective synthesis of Z,E and Z,Z-1,4-dienes has been achieved by the cross-coupling of allylic substrates with vinyl organometallic reagents. Key to this strategy was the development of a method for regiospecific incorporation of a tri-n-butylstannyl group in the gamma-position of the allylic cross-coupling partner. The steric bulk of this moiety ensures the stereochemical integrity of the allylic double bond throughout the coupling sequence and is easily replaced by hydrogen in the coupled product. This strategy has been applied to the synthesis of the termite trail marker pheromone 22 and the leafminer moth sex pheromone 28.