Table 1: Biosynthesis of main compounds classes of herbivore-induced plant volatiles.

Terpenoids
Terpenoids are basically synthesized in three consecutive steps as described by Dudareva et al. [20]: first, formation of the primary C5 units, the isoprene building blocks. Two or more of these C5 units can, in the second step, be condensed into C10 or C15 units which are, in the third step, conversed into the respective mono- or sesquiterpenes. Step two can be skipped to convert a single C5 unit into a hemiterpene. There are two pathways producing the C5 units in plant cells. The MEP pathway is located in the plastids and produces C5 units for hemi-, mono-, and diterpene synthesis. The MVA pathway is located in the cytosol, producing C5 units for sesquiterpene synthesis. Cross talk between these two pathways is happening. Eventually, enzymatic alterations can improve the volatility and/or change functionality of the hemi-, mono-, sesqui-, and diterpenes. The large enzyme family of terpene synthases is responsible for the last steps in terpene biosynthesis, creating an astounding diversity of terpenoids. Volatility decreases with increasing molecule size: hemi- and monoterpenes are considered volatiles while sesquiterpenes are semivolatiles and diterpenes are nonvolatiles.


Benzenoids and phenylpropanoids
The shikimate pathway synthesizes the amino acid L-phenylalanine which is the common precursor of benzenoids and phenylpropanoids which contribute to the HIPV bouquet [2, 17]. After L-phenylalanine is deaminated by the enzyme phenylalanine ammonia-lyase, the resulting trans-cinnamic acid can be transformed into benzoic acid, the precursor of benzenoids, or into phenylpropanol, the precursor of volatile phenylpropenes like eugenol and chavicol. Volatile phenylpropanoids, however, are produced from L-phenylalanine directly. Either way, the final biosynthetic steps are dominated by the enzyme superfamilies of acyltransferases and methyltransferases.

Fatty acid derivatives
The LOX pathway produces derivatives of C18 fatty acids released from damaged cell membranes [20]. Methyl jasmonate and “green leaf volatiles” (GLV) like hexenol and hexenyl acetate are all breakdown products of C18 unsaturated fatty acids like linoleic and linolenic acid [20]. In the first step of the LOX pathway, the fatty acids are stereospecifically oxygenated into 9- or 13-hydroperoxy intermediates, feeding two separate branches of the pathway: methyl jasmonate and C6 GLVs are produced from the 13-hydroperoxy intermediates while C9 GLV are produced from the 9-hydroperoxy intermediates [146].

MEP = methylerythritol phosphate pathway, MVA = mevalonate pathway, LOX = lipoxygenase pathway.