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

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

doi:10.1016/j.tet.2019.03.025

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

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

Research output: Contribution to journal › Article › peer-review

Abstract

A series of five 12-dodecanolides have been synthesised containing CF₂ 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 assess if the analogues may act as mimetics for 12-decenolide pheromones associated with the Emerald Ash Borer. Accordingly individual syntheses of 5,5-difluoro- 5, 6,6-difluoro- 6, 7,7-difluoro- 7, 8,8-difluoro- 8 and 5,5,8,8-tetrafluoro- 9, 12-decanolides is outlined and X-ray structural data was obtained for three (5, 8 and 9) of these compounds. The structures show clearly that the CF₂ groups occupy ‘corner’ locations in the macrocycle consistent with their ability to bias accessible conformations. The fluorine containing 12-dodecanolides all generated an electro-antennogram response in female beetles.

Original language	English
Pages (from-to)	2917-2922
Journal	Tetrahedron
Volume	75
Issue number	21
Early online date	20 Mar 2019
DOIs	https://doi.org/10.1016/j.tet.2019.03.025
Publication status	Published - 24 May 2019

Keywords

Insect pheromones
Emerald ash borer
Organofluorine chemistry
12-Decanolides
Electroantennogram (EAD) analyses

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10.1016/j.tet.2019.03.025

Zhang_2019_Tetrahedron_Fluorine_AAM
Copyright © 2019 Published by Elsevier Ltd. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1016/j.tet.2019.03.025
Accepted author manuscript, 734 KBLicence: CC BY-NC-ND

Fluorine in pheromones: synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics
Zhang, Q. (Creator), Teschers, C. S. (Creator), Callejo, R. (Creator), Yang, M. (Creator), Wang, M. (Creator), Silk, P. J. (Creator), Ryall, K. (Creator), Roscoe, L. E. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator) & O'Hagan, D. (Creator), Cambridge Crystallographic Data Centre, 15 Jan 2019
https://dx.doi.org/10.5517/ccdc.csd.cc21gvhw and 2 more links, https://dx.doi.org/10.5517/ccdc.csd.cc21gvjx, https://dx.doi.org/10.5517/ccdc.csd.cc21gvky (show fewer)
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@article{24c06e69c7ac4c8a987c40ed618ad8f7,

title = "Fluorine in pheromones: synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics",

abstract = "A series of five 12-dodecanolides have been synthesised containing CF2 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 assess if the analogues may act as mimetics for 12-decenolide pheromones associated with the Emerald Ash Borer. Accordingly individual syntheses of 5,5-difluoro- 5, 6,6-difluoro- 6, 7,7-difluoro- 7, 8,8-difluoro- 8 and 5,5,8,8-tetrafluoro- 9, 12-decanolides is outlined and X-ray structural data was obtained for three (5, 8 and 9) of these compounds. The structures show clearly that the CF2 groups occupy {\textquoteleft}corner{\textquoteright} locations in the macrocycle consistent with their ability to bias accessible conformations. The fluorine containing 12-dodecanolides all generated an electro-antennogram response in female beetles.",

keywords = "Insect pheromones, Emerald ash borer, Organofluorine chemistry, 12-Decanolides, Electroantennogram (EAD) analyses",

author = "Qingzhi Zhang and Teschers, {Charlotte S.} and Ricardo Callejo and Mingyan Yang and Mingan Wang and Silk, {Peter J.} and Krista Ryall and Roscoe, {Lucas E.} and Cordes, {David B.} and Slawin, {Alexandra M.Z.} and David O'Hagan",

note = "Authors thank the Engineering and Physical Sciences Research Council (EPSRC) for funding and we are grateful to the EPSRC Mass Spectroscopy Service at the University of Swansea for carrying out some of the accurate mass analysis of prepared compounds.",

year = "2019",

month = may,

day = "24",

doi = "10.1016/j.tet.2019.03.025",

language = "English",

volume = "75",

pages = "2917--2922",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

number = "21",

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TY - JOUR

T1 - Fluorine in pheromones

T2 - synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics

AU - Zhang, Qingzhi

AU - Teschers, Charlotte S.

AU - Callejo, Ricardo

AU - Yang, Mingyan

AU - Wang, Mingan

AU - Silk, Peter J.

AU - Ryall, Krista

AU - Roscoe, Lucas E.

AU - Cordes, David B.

AU - Slawin, Alexandra M.Z.

AU - O'Hagan, David

N1 - Authors thank the Engineering and Physical Sciences Research Council (EPSRC) for funding and we are grateful to the EPSRC Mass Spectroscopy Service at the University of Swansea for carrying out some of the accurate mass analysis of prepared compounds.

PY - 2019/5/24

Y1 - 2019/5/24

N2 - A series of five 12-dodecanolides have been synthesised containing CF2 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 assess if the analogues may act as mimetics for 12-decenolide pheromones associated with the Emerald Ash Borer. Accordingly individual syntheses of 5,5-difluoro- 5, 6,6-difluoro- 6, 7,7-difluoro- 7, 8,8-difluoro- 8 and 5,5,8,8-tetrafluoro- 9, 12-decanolides is outlined and X-ray structural data was obtained for three (5, 8 and 9) of these compounds. The structures show clearly that the CF2 groups occupy ‘corner’ locations in the macrocycle consistent with their ability to bias accessible conformations. The fluorine containing 12-dodecanolides all generated an electro-antennogram response in female beetles.

AB - A series of five 12-dodecanolides have been synthesised containing CF2 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 assess if the analogues may act as mimetics for 12-decenolide pheromones associated with the Emerald Ash Borer. Accordingly individual syntheses of 5,5-difluoro- 5, 6,6-difluoro- 6, 7,7-difluoro- 7, 8,8-difluoro- 8 and 5,5,8,8-tetrafluoro- 9, 12-decanolides is outlined and X-ray structural data was obtained for three (5, 8 and 9) of these compounds. The structures show clearly that the CF2 groups occupy ‘corner’ locations in the macrocycle consistent with their ability to bias accessible conformations. The fluorine containing 12-dodecanolides all generated an electro-antennogram response in female beetles.

KW - Insect pheromones

KW - Emerald ash borer

KW - Organofluorine chemistry

KW - 12-Decanolides

KW - Electroantennogram (EAD) analyses

U2 - 10.1016/j.tet.2019.03.025

DO - 10.1016/j.tet.2019.03.025

M3 - Article

SN - 0040-4020

VL - 75

SP - 2917

EP - 2922

JO - Tetrahedron

JF - Tetrahedron

IS - 21

ER -

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

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

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