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J Org Chem

Title:		Alternate Cyclization Cascade Initiated by Substrate Isomer in Multiproduct Terpene Synthase from Medicago truncatula
Author(s):		Vattekkatte A; Garms S; Boland W;
Address:		"Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology , Beutenberg Campus, Hans-Knoll-Strasse 8, D-07745 Jena, Germany"
Journal Title:		J Org Chem
Year:		2017
Volume:		20170223
Issue:		6
Page Number:		2855 - 2861
DOI:		10.1021/acs.joc.6b02696
ISSN/ISBN:		1520-6904 (Electronic) 0022-3263 (Linking)
Abstract:		"Promiscuity of terpene synthases results in the enormous diversity of terpenes found in nature. Multiproduct sesquiterpene synthase MtTPS5 isolated from Medicago truncatula generates 27 optically pure products from its natural substrate (2E,6E)-farnesyl diphosphate (FDP). In order to study the promiscuity of MtTPS5, (2Z,6E)-FDP, an analogue of presumptive reaction intermediates from natural reaction cascade, was utilized as a substrate. This stereoisomer induced a novel cyclization pathway leading to sesquiterpenes based on humulane, amorphene, and himachalane skeletons. Interestingly, none of these products matched those observed on incubation of MtTPS5 with natural (2E,6E)-FDP. Further determination of the absolute configuration of each product helped rebuild the stereochemical route of the reaction cascade. Interestingly, the presence of only one enantiomer of each product was observed, indicating the highly stereospecific nature of the enzymatic reaction. Substrate promiscuity of terpene synthases provides organism access to novel chemical bouquets of high optical purity by utilizing existing enzymes. The presence of this mechanism was indicated by the presence of these alternate products in natural herbivore-induced volatiles of M. truncatula"
Keywords:		"Alkyl and Aryl Transferases/*chemistry Chromatography, Gas Cyclization Isomerism Medicago truncatula/*enzymology Spectrum Analysis/methods Substrate Specificity;"
Notes:		"MedlineVattekkatte, Abith Garms, Stefan Boland, Wilhelm eng Research Support, Non-U.S. Gov't 2017/02/15 J Org Chem. 2017 Mar 17; 82(6):2855-2861. doi: 10.1021/acs.joc.6b02696. Epub 2017 Feb 23"