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Terpenoid Biosynthesis 219

Monoterpenoids

Sesquiterpenoids

(-)-menthol (+)-carbon (-)-carbon

Nootkatone
Parthenolide
(+)--pinene (-)--pinene

GPP Triterpenoids

squalene
Helenalin 2x
FPP
Thapsigargin

2x 1x
Artemisinin Digitoxigenin (aglycon)

isoprene DMAPP IPP

Diterpenoids
3x
Tetraterpenoids
phytoene

2x GGPP
Taxol

Astaxanthin
FPP+ n x

Salvinorin A

Poly-terpenene

Cis -polyisoprene or natural rubber (MW = 103 -106)

Figure 8.1 Examples of diverse terpenoids used as aroma, avours, medicine, and industrial
chemicals. Condensation rules for mono-, sesqui-, di-, tri-, tetra- and poly-terpenes are depicted
from the basic building blocks, IPP and DMAPP

further extended by sequential condensations with IPP to yield C10 (1 IPP), C15 (2 IPP)
and C20 (3 IPP) diphosphates, referred to as geranyl diphosphate (GPP), farnesyl diphos-
phate (FPP), and gerenylgeranyl diphosphate (GGPP), respectively (Figure 8.3A). These
linear prenyl diphosphate molecules are the direct substrates of terpene synthases (TPSs),
which constitute a superfamily of enzymes responsible for the synthesis of a plethora of
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220 Plant Metabolism and Biotechnology

tail head
Dimethylallyl diphosphate (DMAPP)

C5 Isoprene

Isopentenyl diphosphate (IPP)

B

chrysanthemene
limonene
head-to-tail head-to-middle

squalene

head-to-head

Figure 8.2 Carbon backbones of terpenoids. (A) The structure of the basic building block,
isoprene (left), and structures of DMAPP and IPP (the biological precursors of terpenoids,
right) are illustrated. (B) Different types of isoprene condensation in plant. Grey coloured lines
indicate the C5 isoprene units in the end-products

natural terpene hydrocarbons. By a distinct set of enzymes (squalene synthase and phytoene
synthase) that do not belong to the TPS superfamily, FPP and GGPP can be condensed to
form C30 squalene and C40 phytoene, respectively, from which a diverse array of triter-
penoid and tetraterpenoid derivatives (carotenoids) are synthesized. In addition to IPPs
essential role as a base substrate for small molecules, IPP is the building block of isoprene
polymers such as rubber (cis-polyisoprene). Approximately 2500 plant species, including
the Brazilian rubber tree (Hevea brasiliensis), are able to synthesize terpene polymers. In
these plants, thousands of IPP molecules are conjugated onto the FPP initiator in a unique
cis-configuration. This cis-form accounts for the formation of spring-like structures that