| Title: | "Total synthesis, proof of absolute configuration, and biosynthetic origin of stylopsal, the first isolated sex pheromone of strepsiptera" |
| Author(s): | Lagoutte R; Sebesta P; Jiros P; Kalinova B; Jirosova A; Straka J; Cerna K; Sobotnik J; Cvacka J; Jahn U; |
| Address: | "Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo namesti 2, 166 10 Prague 6, Czech Republic" |
| ISSN/ISBN: | 1521-3765 (Electronic) 0947-6539 (Linking) |
| Abstract: | "The asymmetric total synthesis of the diastereomers of stylopsal establishes the absolute configuration of the first reported sex pheromone of the twisted-wing parasite Stylops muelleri as (3R,5R,9R)-trimethyldodecanal. The key steps for the diastereo- and enantiodivergent introduction of the methyl groups are two different types of asymmetric conjugate addition reactions of organocopper reagents to alpha,beta-unsaturated esters, whereas the dodecanal skeleton is assembled by Wittig reactions. The structure of the natural product was confirmed by chiral gas chromatography (GC) techniques, GC/MS and GC/electroantennography (EAD) as well as field tests. An investigation into the biosynthesis of the pheromone revealed that it is likely to be produced by decarboxylation of a 4,6,10-trimethyltridecanoic acid derivative, which was found in substantial amounts in the fat body of the female, but not in the host bee Andrena vaga. This triple-branched fatty acid precursor thus seems to be biosynthesized de novo through a polyketide pathway with two consecutive propionate-propionate-acetate assemblies to form the complete skeleton. The simplified, motionless and fully host-dependent female exploits a remarkable strategy to maximize its reproductive success by employing a relatively complex and potent sex pheromone" |
| Keywords: | "Aldehydes/*chemical synthesis/chemistry/pharmacology Animals Bees/chemistry Behavior, Animal/drug effects Esterification Female Gas Chromatography-Mass Spectrometry Male Nitriles/chemistry Sex Attractants/*chemical synthesis/chemistry/pharmacology Stereoi;" |
| Notes: | "MedlineLagoutte, Roman Sebesta, Petr Jiros, Pavel Kalinova, Blanka Jirosova, Anna Straka, Jakub Cerna, Katerina Sobotnik, Jan Cvacka, Josef Jahn, Ullrich eng Research Support, Non-U.S. Gov't Germany 2013/05/01 Chemistry. 2013 Jun 24; 19(26):8515-24. doi: 10.1002/chem.201204196. Epub 2013 Apr 29" |
