title: Total synthesis, proof of absolute configuration, and biosynthetic origin of stylopsal, the first isolated sex pheromone of strepsiptera.
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 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.
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo náměstí 2, 166 10 Prague 6, Czech Republic.
authors: Roman
authors: R
authors: Lagoutte
authors: Petr
authors: P
authors: Šebesta
authors: Pavel
authors: P
authors: Jiroš
authors: Blanka
authors: B
authors: Kalinová
authors: Anna
authors: A
authors: Jirošová
authors: Jakub
authors: J
authors: Straka
authors: Kateřina
authors: K
authors: Černá
authors: Jan
authors: J
authors: Šobotník
authors: Josef
authors: J
authors: Cvačka
authors: Ullrich
authors: U
authors: Jahn
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D000818:Animals; D001516:Bees / Q000737:chemistry; D001522:Behavior, Animal / Q000187:drug effects; D004951:Esterification; D005260:Female; D008401:Gas Chromatography-Mass Spectrometry; D008297:Male; D009570:Nitriles / Q000737:chemistry; D012724:Sex Attractants / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism
chemical_list: C581542:3,5,9-trimethyldodecanal; D000447:Aldehydes; D009570:Nitriles; D012724:Sex Attractants