Fig. Biosynihesis of monoterpene derivatives in caraway fruits (a) and wild strawberries (b) [76]. The biosynthesis of carotenoid-derived volatiles is thought to proceed via three steps: an initial dioxygenase cleavage yielding apocarote- nolds, followed by enzymatic transformations of these apocarotencids tothe pokir aroma prec sors, which finally undergo acid-catalyzed eon versions to volatile compounds [77]. In some cases including tomato, petunia and melon, the dioxygenase cleavage step itself can yield 4 vole ate product, such as o- and f-ionone, gerany- lacctone, and pscudoionone, from an array of carotenoid pigments (Fig. 2){78 80] 19 Floral Scents and ut Aromas sped by Notte [EAA sn2c00'3 PRET 3 thecon- version of L-Phe to trans-cinnamie avid by the enzyme L-phenylalanine ammonia-lyase (PAL) (Fig. 1). Trans-cinnamie acid ean undergo methylation to form methyleianamate [81], known component of floral seent, oF can serve as the precursor for a plethora of further inter- mediates such as hydroxyeinnamic acids, alde~ hydes and alcohols, which are formed by a series of hydroxylation and methylation rese~ tions common with the lignin/lignan biosyn- thetic pathway [82]. One of these intermediates, coniferv| alcohol, has been recently shown to serve as the precursor for the synthesis of iso- cugenol in petinia and Clarkia brewert flowers (Fig. 4)[83, 84]. This monoligno] is frst ester fied to coniferyl acetate by the enzymeconiteryl aleobol acyltransferase [85], a member of the BALD family, named for the first four bio~ Phenyipropanoids and Benzenoids Phenylpropanoids and benzenoids constitute the second most ubiquitous class of plant vola- compounds [9] and are derived fiom the amino acid L-phenylalanine (Phe) (Fig. 2) Despite their abundance, diversity, and impor tance in the seent and arome of countless plant species, the precise biochemical pathways lead ing to the formation of volatile phenylpropa- noids and their derivatives are still mostly unknown. The first committed step through the a3 chemically characterized enzymes of this family, BEAT (acoty-CoAzbenzyl aleohol acetylteans- ferase), AHCT (anthocyanin O-hydroxy- cinnamoyltransferase), HCBT (anthranilate Nchydroxycinnamoyl! benzoyltransferase) and DAT (deacetylvindoline 4-0-acetyltransferase) [86]. Tsoeugenol is then produced fiom con ifery| acetate in a reaction catalyzed by isocug= enol synthase [83]. Although eugenol and isoeugenol differ exclusively by the position of the double bond in the propene side chain, in petunia their formation is mediated by two dif ferent and highly divergent NADPH-dependent reductases [84]. In conttast, C, brewer! contains dee distinct NADPH-dependeat reductases, ‘0 of which are responsible for formation and the third possessing isoeugenol syithaie activity, While one BGR syntisec (EGS) isoform is closely related to isocugenolfsoeuzenot oon OSCoA NIL, PAL. pease rar, ‘oc, 7 ‘OCH, on on on L-Phe —trans-Cinnamate p-Coumarate _p-Coumaroyt Coniferyt Conifer Con, alcoho! acetate oe ss b7 och, “Mothylengenol Fig. 4 ranch ofthe phonylpropanoit pathy leading to ee c alcohol acyltransferase; C4H, einamate dehydexylase; (CL, 4-aydroxyeinnamoyl CoA ligase: cubenol synthase; TEMT, (iao)oufonol O-mcthyltmneteracs; (GS, inogugenl synthe; PAL, phen Jalanine ammonia lyase 19° For Scents ad ri Aremaslispivedby Nate phenylacctaldehyde formation [96]. While in tomato phenylacetaldehyde is then con- verted to 2-phenylethanol by the action of 2-phenylacetaldchyde reductase [97], in petu- ‘iba a ls oo ke wily pibcucaie WED plicaletis- nol based on feeding experiments with deuterium-labeled Phe [90], Instead, the largest contribution to 2-phenylethanol formation appeared to come from a different route, possibly through phenylpyravate and phenyllnctic acid as has been recently reported im rose flowers [90, 91, 98]. While the exact biochemical steps leading to the formation of phenylpropanoiés and benzenoids are still mostly unknown, much progress has been achieved in the discovery of enzymes responsi ble for the final steps in the biosynthesis of volatiles in this network [69] ‘ah as Fatty Acid and Amine Acid Derivatives Volatie fay acd derivatives such a es-3-hex- ‘enol, I -hexanal, nonanal, and methyl jasmonate constitte dnote important group of plant vol- ales which are present in the scent and aroma ‘ofnumerous lowers and fruits. Volatile aliphatie (C6 compounds provide fruits and vegetables: With characterise “fresh green” aroma, The compounds originate fiom C18 unsaturated fatty acids (Linoleic or linolenic acids), which enter the “tipoxygenase pilliway” (Fig 1). The first step ofthis pathway isthe dioxygenation of unsaturated fatty acid, catalyzed by liponygon- ase enzymes (LOX) (Fig. 5)[99}. LOX enzymes belong to 0 large family of noabene iin con taining fatty acid dioxygenases. They catalyze the oxygenation of polyenoie fay acids at C9