Applications of Danishefsky’s dienes in asymmetric Oxo-Diels-Alder reactions

Applications of Danishefsky’s dienes in catalytic asymmetric hetero-Diels-Alder (AHDA) reactions or specifically, their asymmetric Oxo-Diels-Alder (AOxo-DA) reactions with appropriate dienophiles are highlighted in detail, including the preparation of catalysts with discussion from a mechanistic points of view. Danishefsky’s dienes are effective and useful compounds for the synthesis of optically active six-membered rings such as dihydropyrones, dihydropyridones and dihydropyrans. Due to the broad range of the overall subject, we have limited ourselves, to the recent developments in the utility of Danishefsky’s dienes in the reaction with carbonyl compounds (aldehydes, ketones and 1,2-dicarbonyl compounds) in asymmetric Oxo-Diels-Alder (AOxo-DA) reactions.     

Pheromone synthesis. Part 244: Synthesis of the racemate and enantiomers of (11Z,19Z)-CH503 (3-acetoxy-11,19-octacosadien-1-ol), a new sex pheromone of male Drosophila melanogaster to show its (S)-isomer and racemate as bioactive

The enantiomers of (11Z,19Z)-3-acetoxy-11,19-octacosadien-1-ol were synthesized from the enantiomers of 3,4-epoxy-1-butanol PMB ether. Its racemate was also synthesized. Its (S)-isomer and racemate were shown to possess the same pheromone activity as CH503, a long-lived inhibitor of male courtship in Drosophila melanogaster, although the racemate was less active.     

Mild, selective deprotection of PMB ethers with triflic acid/1,3-dimethoxybenzene

An efficient method for the cleavage of the p-methoxybenzyl protecting group of several alcohols in the presence of 0.5 equiv of trifluoromethanesulfonic acid and 1,3-dimethoxybenzene in dichloromethane at room temperature is described.