Tatsuji Chuman

Synthesis and absolute stereochemistry of serricornin [(4S,6S,7S)-4,6-dimethyl-7-hydroxy-3-nonanone]: The sex pheromone of the cigarette beetle

Abstract The absolute stereochemistry o serricornin (4,6-dimethyl-7-hydroxy-3-nonanone) was established as 4 S , 6 S , 7 S by synthesizing both (4 S , 6 S , 7 S )-isomer and its antipode. Only the natural enantiomer was bioactive.

Lasioderma chemistry sex pheromone of cigarette beetle (Lasioderma serricorne F.)

A chemical study of the sex pheromone of the cigarette beetle was carried out. Seven components were isolated from active fractions of column chromatography of the female extract, and their structures were elucidated by spectroscopic evidence and confirmed by synthesis to be (4S,6S,7S)-4,6-di-methyl-7-hydroxynonan-3-one (serricornin) (I), 2,6-diethyl-3,5-dimethyl-3,4-dihydro-2H-pyran (anhydroserricornin) (II), 4,6-dimethylnonan-3,7-dione (III), 4,6-dimethylnonan-3,7-diol (IV), 4,6-dimethyl-7-hydroxy-4-nonen-3-one (V), (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(l-methyl-2-oxobutyl)-4H-pyran-4-one (serricorone) (VI) and (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2-hydroxybutyl)-4H-pyran-4-one (serricorole) (VII).These structural features suggested that the occurrence of these components might be related to the polyketide biosynthesis. The behavioral bioassay and BAG experiments revealed the biological role of each component in the copulatory behavior of this insect.

A stereoselective synthesis of “natural” (4S,6S,7S)-serricornin, the sex pheromone of cigarette bettle, from levoglucosenone

Abstract The natural stereoisomer of serricornin was synthesized stereoselectively from levoglucosenone. This firmly established the absolute stereochemistry of serricornin to be 4S,6S,7S. A short synthesis of (−)-δ-multistriatin was also reported.

Absolute stereochemistry of serricornin, the sex pheromone of cigarette beetle, as determined by the synthesis of its (4S,6R,7R)-isomer

Abstract The absolute stereochemistry of serricornin was determined to be (4S,6S,7S) by the synthesis of its (4S,6R,7R)-isomer using a carbohydrate synthon.

4.6-dimethyl-7-hydroxy-nonan-3-one, a sex pheromone of the cigarette beetle (Lasioderma serricorne F.)

Abstract A structure of the sex pheromone produced by the female cigarette beetle (Lasioderma serricorne F.) is established as 4,6-dimethyl-7-hydroxy-nonan-3-one (Ia) by chemical and spectroscopic evidences.

Chiral synthons from levoglucosenone: Short routes for (—)-δ-multistriatin and (+)-prelog-djerassi lactonic acid

Abstract Levoglucosenone ( 1 ) was used as the starting material for short and stereoselective routes to chiral synthons for (—)-δ-multistriatin ( 2 ) and (+)-Prelog-Djerassi lactonic acid ( 3 ). The stereochemistry of these synthons is discussed on the basis of high-resolution 1 H-n.m.r. data.

Determination of the absolute configuration at C-6 and C-7 of serricornin (4,6-dimethyl-7-hydroxy-3-nonanone), the sex pheromone of the cigarette beetle

Abstract The absolute configuration at C-6 and C-7 of serricornin was established as (6 S , 7 S ) by synthesizing its (6 R , 7 S - erythro and (6 R , 7 R - threo isomers.

Inhibitory action of (4S,6S,7R)-isomer to pheromonal activity of serricornin, (4S,6S,7S)-7-Hydroxy-4,6-dimethyl-3-nonanone

By adding the effects of a series of the stereoisomers to the pheromonal activity of serricornin, (4S,6S,7S)-7-hydroxy-4,6-dimethyl-3-nonanone, the sex pheromone of the cigarette beetleLasioderma serricorne (F.) was investigated. The experiments using synthetic enantiomeric mixtures and optically active stereoisomers showed that the (4S,6S,7R)-isomer inhibited significantly the pheromonal activity of serricornin.

Isolation, identification, and synthesis of male-produced sex pheromone of papaya fruit fly,Toxotrypana curvicauda Gerstaecker (Diptera: Tephritidae).

A male-produced sex pheromone of the papaya fruit fly,Toxotrypana curvicauda Gerstaecker, was isolated from volatiles collected from air passed over calling males and was identified as 2-methyl-6-vinylpyrazine by comparative gas-liquid chromatographic and spectroscopic evidence. Synthetic 2-methyl-6-vinylpyrazine elicited typical pheromonal responses from unmated mature female flies such as walking, running, and flying in an arena bioassay; flying upwind with a zigzag flight pattern; and hovering in the pheromone plume in a wind-tunnel bioassay. These responses were similar quantitatively and qualitatively to responses to naturally occurring pheromone from calling male papaya fruit flies.

Identification of female-produced sex pheromone from banded cucumber beetle,Diabrotica balteata leconte (Coleoptera: Chrysomelidae)

A sex pheromone produced by female banded cucumber beetle adults,Diabrotica balteata LeConte, was isolated from volatiles trapped on Porapak Q and identified as 6,12-dimethylpentadecan-2-one. The structure was elucidated by spectroscopic analyses and confirmed by synthesis. The synthesized racemic compound was equal to the purified natural pheromone in eliciting responses by banded cucumber beetle males to field traps. A doseresponse characteristic was demonstrated for the racemic material formulated on filter paper or rubber septa and placed in field traps. The absolute configuration at the C-6 and C-12 positions was not established.