Shiro Satoda

Application of lipase-catalyzed transformations for the synthesis of insect pheromones and related compounds

Abstract This review describes efficient means of preparing optically pure insect pheromones and related compounds via lipase-catalyzed enantioselective reaction on a large scale. (1) A new synthesis of the Japanese beetle pheromone, (R,Z)-(−)-5-(1-decenyl)oxacyclopentan-2-one, established by a combination of two lipase-catalyzed transformation was demonstrated. (2) A chemico-enzymatic procedure for the syntheses of both enantiomers of cupreous chafer beetle pheromone, (R,Z)- and (S,Z)-5-(1-octenyl)oxacyclopentan-2-one, was described. (3) An optical resolution of (±)-2,3-epoxy-8-methyl-1-nonanol, the key intermediate of the synthesis of gypsy moth pheromone, was demonstrated. (4) A practical chemico-enzymatic synthesis of (+)-disparlure in large scale was demonstrated. (5) A facile synthesis of carboxyalkyl acrylate, which is special monomers in the synthesis of the new polymers, by two lipase-catalyzed regioselective reactions was described.

Lipase-catalyzed kinetic resolution of 2,3-epoxy-1-tridecanol and its application to facile synthesis of (+)-disparlure.

Acylation of (+/-)-2,3-epoxy-1-tridecanol with acetic anhydride in diisopropyl ether by porcine pancreatic lipase yielded (2R, 3S)-2,3-epoxy-1-tridecanol as the remaining substrate with an optical purity of over 99% ee. (+)-Disparlure was synthesized in two steps from this optically active epoxy alcohol.

Lipase-catalyzed kinetic resolution of 4-hydroxy-5-dodecynonitrile and its application to facile synthesis of a cupreous chafer beetle sex pheromone

Abstract A facile synthetic method for a cupreous chafer beetle sex pheromone ( R,Z )-(−)-5-(1-octenyl)oxacyclopentan-2-one has been developed by employing lipase-catalyzed enantioselective acylation of racemic 4-hydroxy-5-dodecynonitrile in an organic solvent.

Synthesis of the four possible stereoisomers of 21-methyl-8-pentatriacontene, the female contact sex pheromone of the yellow-spotted longicorn beetle, Psacothea hilaris

Abstract The synthesis of the four possible stereoisomers of 21-methyl-8-pentatriacontene, the ( R )- and ( S )-enantiomers of both ( Z )- and ( E )-geometrical isomers, was achieved by starting from the enantiomers of 3-hydroxy-2-methylpropionate, 1-nonyne and 1,10-decandiol to evaluate the response of the male yellow-spotted longicorn beetle, Psacothea hilaris .