Canadian Forest Service Publications

Fluorine in pheromones: Synthesis of fluorinated 12-dodecanolides as emerald ash borer pheromone mimetics. 2019. Zhang, Q.; Teschers, C.; Cellejo, R.; Yang, M.; Wang, M.; Silk, P.J.; Ryall, K.; Roscoe, L.; Cordes D.; Slawin, A.M.Z.; O'Hagan, D. Tetrahedron. Volume 75. pages: 2917-2922.

Year: 2019

Issued by: Atlantic Forestry Centre

Catalog ID: 40516

Language: English

Availability: PDF (request by e-mail)

Available from the Journal's Web site.
DOI: 10.1016/j.tet.2019.03.025

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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 of 13-membered macrolide 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-dodecanolides are outlined, and X-ray structural data were 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.

Plain Language Summary

A series of five EAB pheromone analogs have been synthesized containing CF2 groups at different carbon positions and, in one case, a double substitution at C5 & C8, as a strategy to bias the conformational space accessed by these macrocyclic pheromones and to assess if the analogs may act as mimics for pheromones associated with the emerald ash borer. Accordingly, individual syntheses of 5,5-difluoro, 6,6-difluoro, 7,7-difluoro, 8,8-difluoro-, and 5,5,8,8-tetrafluoro 12-decanolides is outlined, and X-ray structural data were obtained for three of these compounds. The structures show clearly that the CF2 groups occupy ‘corner’ locations in the pheromone, consistent with their ability to bias accessible ring shapes. The fluorine containing analogs all generated an electro-antennogram response in female beetles.