ISSN:
0170-2041
Keywords:
Oviposition-deterring pheromone
;
Rhagoletis cerasi L.
;
Epoxide opening
;
1,5-Cyclooctadiene-CuCl catalysis
;
Glucosylation
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Synthesis of the Oviposition-Deterring Pheromone of Rhagoletis cerasi L.The oviposition-deterring pheromone of Rhagoletis cerasi L. (-)-(8R,15R)-1 and a mixture of the two compounds (-)-(8R and 8S,15R)-1 have been synthesized. In the presence of the 1,5-cyclooctadiene-CuCl complex as catalyst the Grignard reagent of (-)-(R)-4 reacts with the epoxides (-)-(S)-5 and (±)-5 to give (-)-(7R,14R)-6 and (-)-(7R and 7S,14R)-6. The optically active reagent (-)-(R)-4 has been prepared from ( + )-(R)-1,2-epoxypropane. (-)-(S)-5 has been prepared from L-malic acid dimethyl ester. - After converting the 7-hydroxy groups of (7R,14R)-6 and (7R and 7S,14R)-6 into benzyl ethers 7, treatment with methanolic HCl solvolyzed the silyl ether and tricyclic orthoester groups to give the methyl esters (8R,15R)-20 and (8R and 8S,15R)-20. Next, these compounds were transformed into the benzyl ether-benzyl esters (8R,15R)-21 and (8R and 8S,15R)-21 that could be β-glucosylated in high yields with tetrapivaloyl-α-D-bromoglucose to give (8R,15R)-22 and (8R and 8S,15R)-22. Hydrogenolysis of the benzyl groups in 22 gave the corresponding 8-hydroxy acids that could be activated as mixed anhydrides and reacted with 2-aminoethanesulfonic acid to give the taurinamides (8R,15R)-23 and (8R and 8S,15R)-23. In the last step the pivaloyl groups of the glucose moiety of the molecules were removed by alkaline hydrolysis. Treatment of the hydrolysis products with an Amberlyst 15 (H+ form) ion exchanger and then with ammonia gave (8R,15R)-1 and (8R and 8S,15R)-1 as ammonium salts. The tetraacetyl-β-glucosides (13R)-2 and (13S)-3 have been synthesized and allow to deduce the (15R) configuration for the pentaacetyl derivative of the natural compound 1 by comparing their 1H-NMR spectra.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.1991199101100
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