Enantiomers of methyl substituted analogs of (Z)-5-decenyl acetate as probes for the chirality and complementarity of its receptor inAgrotis segetum 1: Synthesis and structure-activity relationships

Abstract

The enantiomers of analogs of (Z)-5-decenyl acetate, a pheromone component ofAgrotis segetum, substituted by a methyl group in the 2, 3, 4, 7, and 8 positions and dimethyl substituted in the 4,7 positions, have been synthesized and studied by an electrophysiological single-cell technique and by molecular mechanics calculations. The results demonstrate that the electrophysiological activity as well as the ability of the (Z)-5-decenyl acetate receptor to differentiate between enantiomers depends on the position of the methyl substituent. For analogs methyl substituted in the 2, 4, or 8 position, no differences in the activities of the enantiomers could be observed. In contrast, the enantiomers of the 3- and 7-methyl analogs display a significant difference in the activities, theR-enantiomers being more active than theS-enantiomers. From an analysis of the structure-activity results of the enantiomers of the 4,7-dimethyl-substituted analogs, the chiral sense of the alkylchain of the natural pheromone component on binding to its receptor could be deduced.

Characterizing human odorant signals: insights from insect semiochemistry and in silico modelling

“…Varying the alkyl chain length among the analogues of (Z)-5-decenyl acetate led to an extended SAR, suggesting that the terminal alkyl chain requires a specific chain length for interaction with a hydrophobic part of the protein target [40]. Subsequently, the introduction of methyl groups into the carbon chain of (Z)-5-decenyl acetate [41] showed discrimination amongst the ensuing optical isomers [42]. This investigation provided the first SAR example (Figure 5) of a systematic variation in chemical structures and impact on pheromonal activity.…”

Pheromones of Pine Sawflies: Synthesis of a Pure (2S,3R)-3-Methylalkan-2-ol Stereoisomer via an Asymmetric 1,3-Dipolar Cycloaddition; Preparation of a Pheromone Component of Macrodiprion nemoralis

“…Compound 6 was prepared from (2S,4S)-2,4-dimethyloctan-1-ol, which was obtained from the same batch prepared previously in our laboratory 5 (stereoisomeric purity >99.5%), using PPh 3 and Br 2 under standard conditions. 15…”

An analysis of structure fitting and bioactivity between sex pheromone of cotton bollworm, Helicoverpa armigera (Hübner) and its fluorinated analogs

“…Liljefors et al [3,4] researched the sex pheromone of turnip moth, Agrotis segetum by single-cell measurements and molecular mechanics calculations (MM2), and presented a new model of ligand-receptor. Bengtsson et al [5] , Jönsson et al [6][7][8][9] and Wu et al [10] synthesized a series of alkylation and halogenated compounds, investigated the structure-activity relationship among these compounds by single-cell measurements and molecular mechanics calculations (MM2), and verified the model further. Bykhovskaia and Zhorov [11] calculated all the minimum energy conformations (MECs) of two sex pheromones of the American cockroach, Periplaneta americana, and their 11 structural analogs (seven agonists, two antagonists, and two inactive compounds) using the molecular mechanics method.…”