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Terpenes are natural products that are

structurally related to isoprene.


CH3
H2C

CH

CH2

or

Isoprene
(2-methyl-1,3-butadiene)

Myrcene (isolated from oil of bayberry) is


a typical terpene.
CH3
CH3C

CH2
CHCH2CH2CCH
or

CH2

An isoprene unit is the carbon skeleton of


isoprene (ignoring the double bonds)

Myrcene contains two isoprene units.

The isoprene units of myrcene are


joined "head-to-tail."
head

tail

tail head

Classification of Terpenes

Class
Number of carbon atoms
Monoterpene
10
Sesquiterpene
15
Diterpene
20
Sesterpene
25
Triterpene
30
Tetraterpene
40

Representative Monoterpenes

-Phellandrene Menthol
(eucalyptus) (peppermint)

Citral
(lemon grass)

Representative
Sesquiterpenes

a-Selinene (celery)

Representative Diterpenes

Vitamin A

Representative Triterpene

tail-to-tail linkage of isoprene units

Squalene
(shark liver oil)

C15 sesquiterpenoids are derived from farnesyl diphosphate,


which consists of three C5 isoprene units that are joined
head-to-tail
OPP

C20 diterpenoids are derived from geranyl diphosphate,


which consists of four C5 isoprene units that are joined
head-to-tail

OPP

C25 sesterpenoids are derived from geranyl farnesyl


diphosphate, which consists of five C5 isoprene units that
are joined head-to-tail
OPP

C30 triterpenoids and steroids are derived from squalene,


which consists of two C15 farnesyl units that are joined tailto-tail
C40 tetraterpenoids are derived from phytocene, which
consists of two C20 geranylgeranyl units that are joined tailto-tail

The isoprene units in terpenes do not


come from isoprene.
They come from isopentenyl
pyrophosphate.
Isopentenyl pyrophosphate (5 carbons)
comes from acetate (2 carbons) via
mevalonate (6 carbons).

3 CH3COH

CH3

HOCCH2CCH2CH2OH
OH

CH3
H2C

Mevalonic acid
O O

CCH2CH2OPOPOH

Isopentenyl pyrophosphate

Isopentenyl pyrophosphate is interconvertible to


dimethylallyl pyrophosphate.

Isopentenyl pyrophosphate

Dimethylallyl pyrophosphate

Dimethylallyl pyrophosphate has a leaving group


(pyrophosphate) at an allylic carbon; it is reactive
toward nucleophilic substitution at this position.

The key process involves the double


bond of isopentenyl pyrophosphate
acting as a nucleophile toward the allylic
carbon of dimethylallyl pyrophosphate.

OPP +

The carbocation
can lose a
proton to give a
double bond.

The carbocation
can lose a
proton to give a
double bond.

This compound is called geranyl


pyrophosphate. It can undergo hydrolysis of
its pyrophosphate to give geraniol (rose oil).

H2O

Geraniol

This compound is called farnesyl


pyrophosphate.
Hydrolysis of the pyrophosphate
ester gives the alcohol farnesol.

Farnesyl pyrophosphate is extended


by another isoprene unit by reaction
with isopentenyl pyrophosphate.

Rings form by intramolecular


carbon-carbon bond formation.

E double
bond

Z double
bond

Limonene
H

H2O
-Terpineol

-Pinene

-Pinene

3 CH3COH

CH3

HOCCH2CCH2CH2OH
OH

CH3
H2C

Mevalonic acid
O O

CCH2CH2OPOPOH

Isopentenyl pyrophosphate

In a sequence analogous to the early


steps of fatty acid biosynthesis, acetyl
coenzyme A is converted to Sacetoacetyl coenzyme A.
O

CH3CCH2CSCoA
S-Acetoacetyl
coenzyme A

CH3CCH2CSCoA + CH3CSCoA

In the next step, S-acetoacetyl coenzyme A


reacts with acetyl coenzyme A.
Nucleophilic addition of acetyl coenzyme A
(probably via its enol) to the ketone
carbonyl of S-acetoacetyl coenzyme A
occurs.

CH3CCH2CSCoA + CH3CSCoA

HO

CH3CCH2CSCoA
CH2COH
O

Next, the acyl coenzyme A function


is reduced.
The product of this reduction is
mevalonic acid.
HO

CH3CCH2CSCoA
CH2COH
O

HO
CH3CCH2CH2OH
CH2COH
O

HO

CH3CCH2CSCoA
CH2COH
O

Mevalonic
acid

HO

OPO3

CH3CCH2CH2OH

CH3CCH2CH2OPP

CH2COH

CH2COH

The two hydroxyl groups of mevalonic


acid undergo phosphorylation.

OPO3

CH3CCH2CH2OPP

OPO3

CH3CCH2CH2OPP

O

CH2
CH2 C
Isopentenyl
O
Pyrophosphate
Phosphorylation is followed by a novel
elimination involving loss of CO 2 and PO43.