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A chiral synthesis of (+)-lineatin, the aggregation pheromones of Trypodendron lineatum (Olivier), from D-ribonolactone



A chiral synthesis of (+)-lineatin, the aggregation pheromones of Trypodendron lineatum (Olivier), from D-ribonolactone



Journal of Organic Chemistry 5026: 5649-5655



Lineatin, the aggregation pheromone of Trypodendron lineatum (Olivier), has been shown to be (+)-(1R,4S,5R,7R)-3,3,7-trimethyl-2,9-dioxatricyclo 3.3.1.04,7 nonane, (+)-1, by the first stereospecific chiral synthesis. D-Ribonolactone (3) was used to prepare (2S,3R)-2,3-(isopropylidenedioxy)-4-methyl-4- 2-(trimethylsilyl)ethoxy methoxy pentanal (12). Condensation with the cyanophosphonate 7 provided two isomeric .alpha.,.beta.-unsaturated nitriles, 13. Catalytic hydrogenation furnished (3RS,5R,6R)-3-cyano-5,6-(isopropylidenedioxy)-7-methyl-7- 2-(trimethylsilyl)ethoxy methoxy -1,1-dimethoxyoctane (14), which, upon acid-catalyzed hydrolysis, produced the diastereoisomeric mixture 17. Blocking of the hemiacetal function of 17 with a tert-butyldimethylsilyl group, followed by reaction with methanesulfonyl chloride, produced the mixture 22. Acid-catalyzed cyclization of the deprotected hemiacetal 23 yielded (1R,4R,5R,7S)-7-cyano-3,3-dimethyl-4- (methylsulfonyl)oxy -2,9-dioxabicyclo 3.3.1 nonane (24). Intramolecular nucleophilic ring closure provided (1R,4S,5R,7S)-7-cyano-3,3-dimethyl-2,9-dioxatricyclo 3.3.1.04,7 nonane (25). Conversion of the cyano group to a methyl group using diisobutylaluminum hydride, followed by Wolff-Kishner reduction, produced (+)-1. This 16-step synthetic route to (+)-lineatin clearly established the absolute configuration as 1R,4S,5R,7R and produced (+)-lineatin in 2.7% overall yield.

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