Novel Family of Terpene Synthases Evolved from Trans-Isoprenyl Diphosphate Synthases in a Flea Beetle
Novel family of terpene synthases evolved from trans-isoprenyl diphosphate synthases in a flea beetle Franziska Berana,1, Peter Rahfeldb,2, Katrin Luckc, Raimund Nagelc,3, Heiko Vogeld, Natalie Wielsche, Sandra Irmischc,4, Srinivasan Ramasamyf, Jonathan Gershenzonc, David G. Heckeld, and Tobias G. Köllnerc aResearch Group Sequestration and Detoxification in Insects, Max Planck Institute for Chemical Ecology, 07745 Jena, Germany; bDepartment of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, 07745 Jena, Germany; cDepartment of Biochemistry, Max Planck Institute for Chemical Ecology, 07745 Jena, Germany; dDepartment of Entomology, Max Planck Institute for Chemical Ecology, 07745 Jena, Germany; eDepartment of Mass Spectrometry, Max Planck Institute for Chemical Ecology, 07745 Jena, Germany; and fEntomology, AVRDC–The World Vegetable Center, Shanhua, Tainan 74151, Taiwan Edited by Jerrold Meinwald, Cornell University, Ithaca, NY, and approved February 5, 2016 (received for review November 27, 2015) Sesquiterpenes play important roles in insect communication, for monoterpene myrcene in the bark beetle Ips pini represents the example as pheromones. However, no sesquiterpene synthases, only insect terpene synthase known to date (14). the enzymes involved in construction of the basic carbon skeleton, The reactions catalyzed by TPSs involve the generation of a have been identified in insects to date. We investigated the highly reactive carbocation intermediate, which can undergo a wide biosynthesis of the sesquiterpene (6R,7S)-himachala-9,11-diene in array of different cyclizations, hydride shifts, and other rearrange- the crucifer flea beetle Phyllotreta striolata, a compound previously ments. The reaction cascade is either initiated by a metal ion- identified as a male-produced aggregation pheromone in several dependent ionization of the diphosphate moiety or a protonation of Phyllotreta species.
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