Plant-derived flavor

compounds
1
Flavor compounds
Flavor molecules constitute a heterogeneous
group of compounds, with straight-chain,
branched-chain, aromatic and heteroaromatic
backbones
bearing diverse chemical groups such as
hydroxyl, carbonyl, carboxyl, ester, lactone,
amine, and thiol functions. More than 700 flavor
chemicals have been identified and catalogued
2
Natural Aroma Chemicals
large variety of acids,
alcohols,
ketones,
aldehydes,
other organic compounds
Cinnamaldehyde
http://www.hellochem.com/xz/img/img0/986.gif
Ethyl vanillin
http://www.bmrb.wisc.edu/metabolomi
cs/standards/Ethyl_vanillin/lit/jr_167.p
ng
3
Chemical synthesis VS Biosynthesis
Most commercial flavorants are nature identical, which
means that they are the chemical equivalent of natural
flavors but are chemically synthesized, mostly from
petroleum-derived precursors
Bioproduction, including the extraction from natural sources,
de novo microbial processes (fermentation), and bioconversion
of natural precursors using micro-organisms or isolated
enzymes
4
Examples of Natural Aroma Chemicals
Chemical Odor
Diacetyl Buttery
Isoamyl acetate Banana
Benzaldehyde Bitter almond and
cherry
Cinnamic aldehyde Cinnamon
Ethyl propionate Fruity
Methyl anthranilate Grape
5
Examples of Natural Aroma Chemicals
Chemical Odor
Ethyl-(E,Z)-2,4-
decadienoate
Pear
Allyl hexanoate Pineapple
Ethyl maltol Sugar, cotton candy
Ethyl vanillin Vanilla
Methyl salyicyllate Wintergreen
Limonene Orange
6
Biological functions of plant volatiles
Compounds emitted by flowers most probably serve to attract and
guide pollinators
volatiles might also protect the carbohydrate-rich nectar by inhibiting
microbial growth.
vegetative plant tissue release volatiles following herbivore damage.
Some of these substances attract arthropods that prey upon or
parasitize the herbivores.
Volatiles also act as direct repellents or toxicants for herbivores and
pathogens.
In fruits, volatile emission and accumulation facilitate seed dispersal by
animals and insects.
vegetative tissues often produce and release many of the
volatiles after their cells are disrupted. These volatile flavor
compounds may exhibit anti-microbial activity.
associated with defensive and attractive roles
7
Aromatic compounds responsible for odor
and flavor of fruits comprise;
Alcohols
Carbonyls
Acids
Esters
Lactones
Phenols
R-OH
R-
CHO
R-CO-R
R-COOH
R-COO-R
R
O CO
8
Estimated world
consumption of
selected aroma
chemicals in flavor
and fragrance
compositions
CHO
OH
OCH
3
9
10
CO
2
+ H
2
O
Photosynthesis Glucose Carbohydrates
G
L
Y
C
O
L
Y
S
I
S
Acetyl CoA
Citric Acid
Cycle
Fatty Acids
Lipids
Acetogenins
Terpenes
Steroids
Building Blocks
Amino Acids
Proteins
synthesis
enzymes
regulation
Nucleic
Acids
reproduction
Alkaloids
Phenyl-
propanoids
RNA DNA
PRIMARY METABOLISM
SECONDARY
METABOLISM
SECONDARY
METABOLISM
hn
CO
2
+ H
2
O + ATP
Flavonoids
11
O
CH
2
OH
OH
OH
OH
O H
CO
2
hn
photosynthesis
Glucose
(6 carbons)
O
CH
2
OH
O
OH
OH
O H
O
CH
2
OH
O
OH
OH
O
CH
2
OH
O
OH
OH
starch
n
glycolysis
C H
CH
2
OP
OH
CHO
C OP
CH
2
COOH
C
CH
2
OP
O
CH
2
OH
phosphoenol
pyruvate (PEP)
(3 carbons)
C H
3
C
O
SCoA
acetyl-
coenzymeA
(2 carbons)
citric
acid
cycle
energy (ATP)
+ CO
2
+ H
2
O
C H
3
C
O
CH
2
C
O
CH
2
polyketides
acetogenins
lipids
fatty acids
mevalonic
acid
terpenes
steroids
carotenoids
O
O
O H CH
3
CH OH
CH OH
CH
2
OP
CHO
erythrose-
4-phosphate
COOH
O H OH
OH
shikimic
acid
NH
2
COOH
anthanilic
acid
phenylalanine
tyrosine
alkaloids
tryptophan
oxalo-
acetate
lysine
ornithine
aspartic
acid
nicotinic
acid
phenylpropanes
glutamic acid
NH
3
12
Amino acid synthesis
13
isoprenoid biosynthesis proceeds either via the
"classical" or most well studied, mevalonate pathway
(cytosolic) (for the synthesis of sterols, sesquiterpenes,
triterpenoids)
or via the non-mevalonate (1-deoxy-D-xylulose-5-
phosphate, DXP) pathway for plastidic isoprenoids
(carotenoids, phytol [side-chain of chlorophylls], plastoquinone,
isoprene, monoterpenes and diterpenes).
14
15
16
Biosynthesis of flavors in vegetables and fruits
develop when tissue damage occurs
(Intact vegetable generally contains few
volatiles)
Vegetable flavors
are formed during brief ripening period
Fruit flavors
17
Minute quantities of lipids, CHO, protein (amino
acids) are enzymatically converted to volatile
flavors.
BIOGENESIS OF FRUIT AROMA
develops entirely during ripening period of plant
18
FRUIT FLAVOR COMPOUNDS
Apple n-hexanal, ethyl butyrate, 1-propyl propionate, 1-
butyl acetate, trans-2-hexenal, ethyl 2-
methylbutyrate, 2-methylbutyl acetate, 1-hexanol,
hexen-1-ol, trans-2-hexen-1-ol, hexyl acetate,
Esters; alcohols; aldehydes; ketone; acids; including
hexanal; ethyl 2-methyl butyrate

Banana
alcohols; esters, including amyl acetate, isoamyl
acetate, butyl butyrate, amyl butyrate

Peach Ethyl acetate, dimethyl disulfide, cis-3-hexenyl
acetate, methyl octanoate, ethyl octanoate, 6-pentyl
alpha pyrone, gamma decalactone
19
Lipids Polysaccharide Proteins/Enzymes Lignins
Aliphatic Terpenes
Methyl-Branched
Aromatic
Acids
Alcohols
Esters
Carbonyls
lactones
Sesquiterpenes
Hydrocarbons
Alcohols
Carbonyls
monoterpenes
Alcohols
Acids
Esters
carbonyls
Alcohols
Acids
Esters
carbonyls
Biosynthesis of fruit volatiles
Carbohydrate
Amino acid
Cinnamic acid
Terpene
Fatty acid
Acetyl-CoA
Malonyl CoA
Acetyl CoA
Pyruvate
Mevalonyl CoA
Shikimic acid
20
Flavorants from carbohydrate metabolism
Furanones and pyrones

fruit constituents
Only a limited number of natural volatiles
originate directly from carbohydrates without
prior degradation of the carbon skeleton.
21
Furanones and pyrones
Carbohydrate-derived flavor molecules, including 4-hydroxy-2,5-dimethyl-3(2H)-
furanone (furaneol), 2,5-dimethyl-4-methoxy-3(2H)-furanone (methoxyfuraneol), 4-
hydroxy-5-methyl-3(2H)-furanone (norfuraneol), 2-ethyl-4-hydroxy-5-methyl-3(2H)-
furanone (homofuraneol), 4-hydroxy-2-methylene-5-methyl-3(2H)- furanone (HMMF)
and 3-hydroxy-2-methyl-4H-pyran-4-on (maltol).
22
Glycolysis
Glucose (6C)

2 Pyruvate (3C)
Ethanol Lactate
TCA Cycle/
Citric Cycle
CO
2
+O
2
-O
2
-O
2
Flavorants from carbohydrate metabolism
23
Pyruvic acid CH
3
COCOOH
Acetic acid CH
3
COOH
Acetyl CoA CH
3
COSCoA
+ CO
2
Malonyl CoA HOOCCH
2
COSCoA
Malonic Acid HOOCCH
2
COOH
24
the most interesting is terpene biosynthesis
Terpenoids are enzymatically synthesized from acetyl CoA and
pyruvate provided by the carbohydrate pools in plastids and the
cytoplasm.
Terpenoids constitute one of the most diverse families of
natural products, with over 40 000 different structures of
terpenoids
Many of the terpenoids produced are non-volatile and are
involved in important plant processes such as membrane
structure (sterols), photosynthesis (chlorophyll side chains,
carotenoids), redox chemistry (quinones) and growth regulation
(gibberellins, abscisic acid, brassinosteroids)
Flavorants from carbohydrate metabolism
25
Important plant-derived volatile terpenoids.
26
Biosynthesis of Terpenes
isoprene is derived from acetyl-CoA
27
C
CH
2
CH
2
C H
3
O H C
C
O
O
SCoA
SCoA
3 acetylCoA
C
CH
2
CH
2
C H
3
O H C
C
O
O
SCoA
SCoA
H
C
CH
2
CH
2
C H
3
O H C
C
O
O
SCoA
H
C
CH
2
CH
2
C H
3
O H C
CH
2
O
SCoA
OH
C
CH
2
CH
2
C H
3
O H C
CH
2
O
OH
OH
mevalonic acid
MEVALONIC ACID PATHWAY
FORMATION OF MEVALONIC ACID FROM ACETYL UNITS
NADPH
NADPH
H
2
O
..
: :
-
(continued next slide)
28
CH
2
C
S
O
CoA C
O
O H
C
O
CH
3
S CoA
- CO
2
CH
2
C
S CoA
C
CH
3
O
O
..
CH
2
C
CH
2
O
C
O
C
C H
3
O
SCoA
POLYKETIDE CHAINS
1 2
CH
2
C
S CoA
C
CH
3
O
O
CH
2
C
O
SCoA
H
CH
2
CH
2
CH
2
CH
2
C
OH
CH
3
COOH
O H
mevalonic acid
TERPENES ACETOGENINS STEROIDS
THERE ARE TWO CARBONYL GROUPS IN THE 2-UNIT POLYKETIDE CHAIN
EITHER ONE CAN REACT
LINEAR
BRANCHED
29
C
CH
2
CH
2
C H
3
O H C
CH
2
O
OH
OH
mevalonic acid
C
CH
2
CH
2
C H
3
O C
CH
2
O
O
O
P H
P P
:B-Enz
2 ATP
ADP
AMP
CH
2
H
CH
2
CH
3
O P P
CH
3
H
CH
2
CH
3
O P P
3,3-dimethylallyl
pyrophosphate
isopentenyl
pyrophosphate
Enz-B:
H
+
MEVALONIC ACID PATHWAY
The isopentenyl and 3,3-dimethylallyl pyrophosphate intermediates
These five-carbon
intermediates are
responsible for the
formation of all the
terpenes.
DMAPP IPP
30
Classification of Terpenes
31
Apocarotenoid formation
Carotenoid substrates are oxidatively cleaved to yield the apocarotenoid derivatives
(right).
32
Some of the volatile organic compounds in wine come from the grape's skin, or
exocarp, while others come from the grape's flesh, or mesocarp. Organic acids give
wine its tartness, and sugars give it sweetness. Terpenes provide floral or fruity
flavors. Norisoprenoids impart a honeylike character. Thiols are the sulfur-based
compounds behind complex wine aromas such as guava, passionfruit or grapefruit
but when thiols go wrong, they can make a wine taste "funky."
33
products; acids, alcohols, diketones, ketones, esters of these compounds.
Lipids
metabolic pathway for lipid biosynthesis plays
a significant role in flavor formation.
Alpha-, Beta-oxidation
Oxidation via lipoxygenase
34
Lipoxygenase activity is believed to be the
major source of volatiles in plants.
Oxidation via Lipoxygenase
Major products: volatile C6 and C9 aldehydes and alcohols
Substrate: unsaturated fatty acid (linoleic and linolenic acids).
Lipoxygenase enzymes (dioxygenase) catalyze reactions
between O
2
and polyunsaturated fatty acids
35
Linolenic acid-derived flavor molecules.
AAT, alcohol acyl CoA transferase; ADH, alcohol dehydrogenase; AER, alkenal
oxidoreductase; AOC, allene oxide cyclase; AOS, allene oxide synthase; HPL,
hydroperoxide lyase; JMT, jasmonate methyltransferase; LOX, lipoxygenase; OPR, 12-
oxo-phytodienoic acid reductase; 3Z,2E-EI, 3Z,2E-enal isomerase. 36
Fatty acid precursors (Tomato)
37
- and -oxidation of fatty acids
Palmitoyl-CoA (16:0)
Myristoyl-CoA (14:0)
+ Acetyl-CoA
the specific pathways in plants are not well understood
38
Formation of pear flavors via beta-oxidation
39
Lactones
40
Amino Acid Metabolism
Amino acid metabolism yields short chain aliphatic and
aromatic alcohols, acids, carbonyls and esters
They are the primary source of branched chain
aliphatic flavor compounds
their pathways have been barely analyzed in plants.
41
42
amino acid precursors
(Tomato)
43
(a) Catabolism of branched-chain amino acids leading to methyl branched flavor compounds, and
(b) postulated biosynthesis of sotolon. Formation of aldehyde (a) from amino acids requires the
removal of both carboxyl and amino groups. The sequence of these removals is not fully known
and could be the opposite to that shown or aldehyde could be formed in one step by aldehyde
synthase
Biosynthesis of amino acid-derived
flavor compounds
44
Starting amino acids: Tyrosine and phenylalanine products:
phenolic/spicy in character
45
Shikimic acid formation
46
Vegetable Flavors
47
Vegetable flavors
flavor again arises from major metabolic processes -
e.g. Lipids, CHO & amino acids.
The role or importance of S compounds to
vegetable flavor is quite significant.
the precursors, enzymes and end flavors are quite
different from fruits.
48
Nonvolatile Precursors
Linoleic, Linolenic acid Thioglucosinolates Cysteine-sulfoxides Methyl-methionine
Precursor-splitting Enzymes
Lypoxygenase Thioglucosidases C-S-lyases None (Heating)
Carbonyls
Alcohols
Oxo-acids
Isothiocyanates
Nitriles
S C O
Thiocyanates
Polysulides
Alkyl-
thosulfinates
CH
3
-S-CH
3
Carbohydrate
Fatty acid Amino acid
Formation of flavor in vegetables
49
Vegetable Flavor Categories


Genus Allium
Enzymes produce volatiles from derivatives
of cysteine (sulfoxides)



Genus Brassica
Enzymes produce volatiles from glucosinolates
50
Alliaceous vegetables
garlic (Allium sativum L.)
onion (Allium cepa L.)
chive (Allium schoenoprasum L.)
leek (Allium porrum L.)
51
Characteristic flavors
not exist in the bulb before processing
are produced when the cellular tissues are
ruptured by cutting or chewing
flavor is produced very rapidly by the action
of an enzyme on the odorless precursors which
coexist in the cells
52
Onion and Garlic Flavor
Enzymatic reaction of cysteine derivative
53
54
55
Glucosinolate precursors are important to the
flavor of both the Brassica and Cruciferae family

Cruciferae family includes radish, horseradish,
mustard.
GLUCOSINOLATES
56
thiocyanate, nitrile, or isothiocyanate
& glucose
Hydrolysis of the glucosinolate
glucosinolate
thioglucosidase
57
58
59
Natural carbon pools for the production
of flavor compounds, and the pathways
60