4.2.1.B8	(9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoic acid	poor substrate	Convallaria majalis	?	-	?	407613	
4.2.1.B8	(9Z,11E,13R)-13-hydroperoxy-9,11-octadecadienoate	is utilized more slowly than (9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	407617	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	-	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate is the preferred substrate	Convallaria majalis	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	an essentially complete loss of isotope is noted with the (14R)-deuterated precursor, whereas incubation of the (14S)-deuterated precursor affords products that retain most of the deuterium label	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	an essentially complete loss of isotope is noted with the (14R)-deuterated precursor, whereas incubation of the (14S)-deuterated precursor affords products that retained most of the deuterium label	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	no activity with (9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoate	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	the enzyme uses preferentially 13-hydroperoxides as substrates and efficiently converts them into divinyl ether fatty acids	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etheroleic acid	?	406971	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoate	the S enantiomer is a much better substrate for the divinyl ether synthase compared to the R enantiomer. Incubation of (9Z,11E,13S)-[18O2]hydroperoxy-9,11-octadecadienoic acid leads to the formation of etheroleic acid which retains 18O in the ether oxygen. An intermediary role of an epoxyallylic cation in etheroleic acid biosynthesis is postulated	Allium sativum	(9Z,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + (9E,11E)-12-[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	two isomers of etheroleic acid are isolated	?	407619	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoic acid	-	Ranunculus acris	(9Z,11E)-12-[(1'Z)-hexenyloxy]-9,11-dodecadienoic acid	i.e. (omega5Z)-etherolenic acid	?	429105	
4.2.1.B8	(9Z,11E,13S)-13-hydroperoxy-9,11-octadecadienoic acid	i.e. 13-HPOD	Selaginella moellendorffii	(9Z,11E)-12[(1E)-hex-1-en-1-yloxy]dodeca-9,11-dienoic acid + H2O	-	?	444107	
4.2.1.B8	(9Z,11E,13S,15Z)-13-hydroperoxy-9,11,15-octadecatrienoate	-	Allium sativum	(9Z,11E)-12-[(1E,3Z)-hexa-1,3-dien-1-yloxy]dodeca-9,11-dienoic acid + H2O	i.e. etherolenic acid	?	407623	
4.2.1.B8	(9Z,11E,13S,15Z)-13-hydroperoxy-9,11,15-octadecatrienoate	highly preferred substrate	Ranunculus acris	(9Z,11E)-12-[(1'Z,3'Z)-hexadienyloxy]-9,11-dodecadienoate + H2O	i.e. etherolenic acid	?	429103	
4.2.1.B8	(9Z,11E,13S,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid	i.e. 13-HPOT	Selaginella moellendorffii	(9Z,11E)-12[(1Z,3Z)-hexa-1,3-dien-1-yloxy]dodeca-9,11-dienoic acid + H2O	-	?	444112	
4.2.1.B8	additional information	irrespective of which hydroperoxide regioisomer serves as the substrate, divinyl ether synthases abstracting the pro-R hydrogen generate divinyl ethers having an E vinyl ether double bond, whereas enzymes abstracting the pro-S hydrogen produce divinyl ethers having a Z vinyl ether double bond	Allium sativum	?	-	?	89	
4.2.1.B8	additional information	low activity with 13-hydroperoxy-octadecatrienoate	Allium sativum	?	-	?	89	
4.2.1.B8	additional information	preferred substrates of the enzyme are the 13-hydroperoxides of alpha-linolenic and linoleic acids, which are converted to the divinyl ether oxylipins (omega5Z)-etherolenic acid, (9Z,11E)-12-[(1?Z,3?Z)-hexadienyloxy]-9,11-dodecadienoic acid, and (omega5Z)-etheroleic acid, (9Z,11E)-12-[(1?Z)-hexenyloxy]-9,11-dodecadienoic acid, respectively, as revealed by the data of mass spectrometry, NMR and UV spectroscopy	Ranunculus acris	?	-	?	89	
4.2.1.B8	additional information	no activity with (9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoic acid and (9S,10E,12Z,15Z)-9-hydroperoxy-10,12,15-octadecatrienoic acid, high substrate specificity, overview. Product identification by GC-MS analyses	Ranunculus acris	?	-	?	89	
4.2.1.B8	additional information	products are analyzed by gas chromatography-mass spectrometry, individual oxylipins are purified by HPLC and finally identified by their NMR data, including the 1H NMR, 2D-COSY, HSQC and HMBC, overview. Enzyme CYP74M3 (SmDES2) converts 13-HPOT and 13-HPOD mainly to etherolenic and etheroleic acids, respectively, via an (E)-vinyl ether radial intermediate. The enzyme is inactive towards (9S,10E,12Z,15Z)-9-hydroperoxy-10,12,15-octadecatrienoic acid (9-HPOT) and (9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoic acid (9-HPOD)	Selaginella moellendorffii	?	-	?	89