Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera

0394753 - ÚOCHB 2014 RIV DE eng J - Článek v odborném periodiku
Lagoutte, Roman - Šebesta, Petr - Jiroš, Pavel - Kalinová, Blanka - Jirošová, Anna - Straka, J. - Černá, K. - Šobotník, Jan - Cvačka, Josef - Jahn, Ullrich
Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera.
Chemistry - A European Journal. Roč. 19, č. 26 (2013), s. 8515-8524. ISSN 0947-6539. E-ISSN 1521-3765
Grant CEP: GA ČR GAP506/10/1466
Institucionální podpora: RVO:61388963
Klíčová slova: asymmetric synthesis * configuration determination * pheromones * total synthesis * Wittig reactions
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 5.696, rok: 2013

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 ,-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.
Trvalý link: http://hdl.handle.net/11104/0223105