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Synthese der Markierungssubstanz der Kirschenfruchtfliege Rhagoletis cerasi L.
Author(s) -
Küchler Birgit,
Voß Gundula,
Gerlach Hans
Publication year - 1991
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.1991199101100
Subject(s) - chemistry , hydrogenolysis , ether , reagent , orthoester , silyl ether , pheromone , medicinal chemistry , silylation , stereochemistry , organic chemistry , catalysis , botany , biology
Synthesis of the Oviposition‐Deterring Pheromone of Rhagoletis cerasi L. The oviposition‐deterring pheromone of Rhagoletis cerasi L. (−)‐(8 R ,15 R )‐ 1 and a mixture of the two compounds (−)‐(8 R and 8 S ,15 R )‐ 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 ,14 R )‐ 6 and (−)‐( 7R and 7S ,14 R )‐ 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 ,14 R )‐ 6 and ( 7R and 7S ,14 R )‐ 6 into benzyl ethers 7 , treatment with methanolic HCl solvolyzed the silyl ether and tricyclic orthoester groups to give the methyl esters (8 R ,15 R )‐ 20 and (8 R and 8 S ,15 R )‐ 20 . Next, these compounds were transformed into the benzyl ether–benzyl esters (8 R ,15 R )‐ 21 and (8 R and 8 S ,15 R )‐ 21 that could be β‐glucosylated in high yields with tetrapivaloyl‐α‐ D ‐bromoglucose to give (8 R ,15 R )‐ 22 and (8 R and 8 S ,15 R )‐ 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 (8 R ,15 R )‐ 23 and (8 R and 8 S ,15 R )‐ 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 (8 R ,15 R )‐ 1 and (8 R and 8 S ,15 R )‐ 1 as ammonium salts. The tetraacetyl‐β‐glucosides (13 R )‐ 2 and (13 S )‐ 3 have been synthesized and allow to deduce the (15 R ) configuration for the pentaacetyl derivative of the natural compound 1 by comparing their 1 H‐NMR spectra.