Fluorine in pheromones: Synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics

Zhang, Qingzhi; Teschers, Charlotte S.; Callejo, Ricardo; Yang, Ming‐Yan; Wang, Mingan; Silk, Peter J.; Ryall, Krista; Roscoe, Lucas E.; Cordes, David B.; Slawin, Alexandra M. Z.; O’Hagan, David

doi:10.1016/j.tet.2019.03.025

Cited by 5 publications

(4 citation statements)

References 33 publications

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“…X-ray structural data was obtained for three ( 5 , 8 and 9 ) of these compounds [46]. The structures show that the CF 2 groups indeed do occupy ‘corner’ positions in the macrocycle consistent with their ability to bias accessible conformations (Figure 4).…”

Section: Pheromone Analogsmentioning

confidence: 90%

“…Continued studies should include work on host compounds (e.g., (3Z)-hexenol and 7- epi -sesquithujene) but also the affinity of the female-produced sex pheromone (3Z)-12-dodecenolide [13,39], a range of structural analogs, including CF 2 fluoro-analogs as pheromone mimetics [46] and the contact-active compounds [8,15].…”

Section: Progress In Identifying Odor Processing Genes In Eabmentioning

confidence: 99%

“…The larger size of fluorine over hydrogen also avoids transannular interactions relative to hydrogen, while the electronegativity of fluorine changes the hybridization towards sp 2 at the directly bound carbon widening the C-CF 2 -C angle [76]. Hence, five 12-dodecanolides (Figure 3) were synthesized containing CF 2 groups at C5, C6, C7, C8 and in one case a double substitution at C5 & C8, as a strategy to bias the conformational space accessed by these macrocycles and to determine if the analogs act as mimetics for 12-dodecanolide pheromones associated with the EAB [46]. The CF 2 group would place conformational constraints at different locations into these molecules, as an alternative strategy to introducing double bonds of defined geometry such as is found in 2 and 3 .…”

Section: Pheromone Analogsmentioning

confidence: 99%

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Semiochemical and Communication Ecology of the Emerald Ash Borer, Agrilus planipennis (Coleoptera: Buprestidae)

Silk

Mayo

Ryall

et al. 2019

Insects

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Knowledge of buprestid chemical ecology is sparse but the appearance of the invasive pest Agrilus planipennis Fairmaire in North America has provided the impetus to study in detail the semiochemistry and ecology of this important buprestid. The macrocyclic lactone (3Z)-12-dodecenolide [(3Z)-lactone] is identified as a key antennally-active compound that is produced by females and attracts males. Though a weak trap attractant alone, when combined with the host kairomone (3Z)-hexenol and the important visual cue of a green canopy trap, significant increases in male trap capture occur, thus defining (3Z)-lactone as both a sex pheromone of A. planipennis as well as the first and only known buprestid pheromone. The non-natural stereoisomer (3E)-12-dodecenolide and the saturated analog, 12-dodecanolide also exhibit mimetic activities towards male A. planipennis, suggesting a notable plasticity in this pheromonal structural motif. Efficient synthetic routes to these compounds have been developed. A series of fluoro-12-dodecanolides has also been synthesized containing CF2 groups as a strategy to bias the conformational space accessed by these macrolides and to assess if the analogs may act as mimetics for 12-dodecanolide pheromones associated in A. planipennis. These compounds also afford a unique opportunity to study the binding affinities of lactone surrogates with A. planipennis chemosensory proteins and olfactory receptors. Some progress has also been made in identifying the genes involved in the reception, processing and degradation of volatiles in this invasive insect. It is now evident that the behavior and ecology of A. planipennis involves a complex pattern of sensory modalities, including visual, tactile, olfactory and potentially acoustic components. Earlier reviews focused on studies of attractive host volatiles in development of a trapping system for early detection and visual and contact phenomena in A. planipennis mate finding. This review will update the semiochemistry and chemical ecology of A. planipennis and discuss studies on chemistry and behavior that have identified female-produced pheromone components and host kairomones.

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Section: Pheromone Analogsmentioning

confidence: 90%

Section: Progress In Identifying Odor Processing Genes In Eabmentioning

confidence: 99%

Section: Pheromone Analogsmentioning

confidence: 99%

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Semiochemical and Communication Ecology of the Emerald Ash Borer, Agrilus planipennis (Coleoptera: Buprestidae)

Silk

Mayo

Ryall

et al. 2019

Insects

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“…However, some of the effects of fluorine substitution are relatively straightforward to interpret such as the ability of fluorinated molecules to suppress metabolism relative to their hydrocarbon analogues. Moreover, organo-fluorine compounds are biologically and chemically more stable than the corresponding chlorine and bromine containing compounds [ 21 ].…”

Section: Introductionmentioning

confidence: 99%

A Fluorinated Analogue of Marine Bisindole Alkaloid 2,2-Bis(6-bromo-1H-indol-3-yl)ethanamine as Potential Anti-Biofilm Agent and Antibiotic Adjuvant Against Staphylococcus aureus

et al. 2020

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Methicillin resistant Staphylococcus aureus (MRSA) infections represent a major global healthcare problem. Therapeutic options are often limited by the ability of MRSA strains to grow as biofilms on medical devices, where antibiotic persistence and resistance is positively selected, leading to recurrent and chronic implant-associated infections. One strategy to circumvent these problems is the co-administration of adjuvants, which may prolong the efficacy of antibiotic treatments, by broadening their spectrum and lowering the required dosage. The marine bisindole alkaloid 2,2-bis(6-bromo-1H-indol-3-yl)ethanamine (1) and its fluorinated analogue (2) were tested for their potential use as antibiotic adjuvants and antibiofilm agents against S. aureus CH 10850 (MRSA) and S. aureus ATCC 29213 (MSSA). Both compounds showed antimicrobial activity and bisindole 2 enabled 256-fold reduction (ΣFICs = 0.5) in the minimum inhibitory concentration (MIC) of oxacillin for the clinical MRSA strain. In addition, these molecules inhibited biofilm formation of S. aureus strains, and compound 2 showed greater eradicating activity on preformed biofilm compared to 1. None of the tested molecules exerted a viable but non-culturable cells (VBNC) inducing effect at their MIC values. Moreover, both compounds exhibited no hemolytic activity and a good stability in plasma, indicating a non-toxic profile, hence, in particular compound 2, a potential for in vivo applications to restore antibiotic treatment against MRSA infections.

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Fluorinated Rings: Conformation and Application

Mondal

Agbaria

Nairoukh

2021

Chemistry A European J

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The introduction of fluorine atoms into molecules and materials across many fields of academic and industrial research is now commonplace, owing to their unique properties. A particularly interesting feature is the impact of fluorine substitution on the relative orientation of a C−F bond when incorporated into organic molecules. In this Review, we will be discussing the conformational behavior of fluorinated aliphatic carbo‐ and heterocyclic systems. The conformational preference of each system is associated with various interactions introduced by fluorine substitution such as charge‐dipole, dipole‐dipole, and hyperconjugative interactions. The contribution of each interaction on the stabilization of the fluorinated alicyclic system, which manifests itself in low conformations, will be discussed in detail. The novelty of this feature will be demonstrated by presenting the most recent applications.

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Fluorine in pheromones: Synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics

Cited by 5 publications

References 33 publications

Semiochemical and Communication Ecology of the Emerald Ash Borer, Agrilus planipennis (Coleoptera: Buprestidae)

Semiochemical and Communication Ecology of the Emerald Ash Borer, Agrilus planipennis (Coleoptera: Buprestidae)

A Fluorinated Analogue of Marine Bisindole Alkaloid 2,2-Bis(6-bromo-1H-indol-3-yl)ethanamine as Potential Anti-Biofilm Agent and Antibiotic Adjuvant Against Staphylococcus aureus

Fluorinated Rings: Conformation and Application

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