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- Title
Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera.
- Authors
Lagoutte, Roman; Šebesta, Petr; Jiroš, Pavel; Kalinová, Blanka; Jirošová, Anna; Straka, Jakub; Černá, Kateřina; Šobotník, Jan; Cvačka, Josef; Jahn, Ullrich
- 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 (3 R,5 R,9 R)-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 α,β-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.
- Subjects
STREPSIPTERA; CHEMICAL synthesis; PHEROMONES; ELENCHIDAE; SEMIOCHEMICALS
- Publication
Chemistry - A European Journal, 2013, Vol 19, Issue 26, p8515
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201204196