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Terpenes
Terpenes are natural products that are structurally related to isoprene. CH3
H2C C CH CH2 or
Isoprene (2-methyl-1,3-butadiene)
Terpenes
CH2
The Isoprene Unit An isoprene unit is the carbon skeleton of isoprene (ignoring the double bonds)
The Isoprene Unit The isoprene units of myrcene are joined "headto-tail." head tail
tail head
Monoterpene
Sesquiterpene Diterpene Sesterpene Triterpene
10
15 20 25 30
Tetraterpene
40
OH
O H
OH
O H
H
a-Selinene (celery)
H
a-Selinene (celery)
a-Selinene (celery)
OH
Vitamin A
OH
Vitamin A
Vitamin A
CH3
CH3 H2C
O O
CCH2CH2OPOPOH
Isopentenyl pyrophosphate
Isopentenyl Pyrophosphate
CH3
H2C
O O
or OPP
CCH2CH2OPOPOH
Isopentenyl pyrophosphate
Isopentenyl and Dimethylallyl Pyrophosphate Isopentenyl pyrophosphate is interconvertible with 2-methylallyl pyrophosphate.
OPP
Isopentenyl pyrophosphate
OPP
Dimethylallyl pyrophosphate
Dimethylallyl pyrophosphate has a leaving group (pyrophosphate) at an allylic carbon; it is reactive toward nucleophilic substitution at this position.
OPP
The key process involves the double bond of isopentenyl pyrophosphate acting as a nucleophile toward the allylic carbon of dimethylallyl pyrophosphate.
OPP
OPP + OPP
OPP The carbocation can lose a proton to give a double bond. + OPP H +
OPP This compound is called geranyl pyrophosphate. It can undergo hydrolysis of its pyrophosphate to give geraniol (rose oil).
OPP H2 O
OH Geraniol
OPP
OPP
From 10 Carbons to 15
OPP
OPP
From 10 Carbons to 15
OPP
From 15 Carbons to 20
OPP
OPP Farnesyl pyrophosphate is extended by another isoprene unit by reaction with isopentenyl pyrophosphate.
Limonene H
+ +
OH
H2O a-Terpineol
Bicyclic Terpenes
+
a-Pinene b-Pinene
Recall O 3 CH3COH
CH3
CH3 H2C
O O
CCH2CH2OPOPOH
Isopentenyl pyrophosphate
In a sequence analogous to the early steps of fatty acid biosynthesis, acetyl coenzyme A is converted to S-acetoacetyl coenzyme A.
CH3CCH2CSCoA
S-Acetoacetyl coenzyme A
CH3CCH2CSCoA + CH3CSCoA
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
CH3CCH2CSCoA CH2COH O
OPO3
CH3CCH2CH2OPP
CH2COH O
OPO3
CH3CCH2CH2OPP CH2 O C O
CH3CCH2CH2OPP CH2 C O
O
CH3CCH2CH2OPP CH2
CH3
CH3 H2C
O O
CCH2CH2OPOPOH
Isopentenyl pyrophosphate
Biosynthetic pathway is based on experiments with 14C-labeled acetate Citronellal biosynthesized using 14C-labeled acetate as the carbon source had the labeled carbons in the positions indicated. O CH3COH H2C CH3 O O
CCH2CH2OPOPOH
O
H