Chapter 26 - Lipids

Terpene and Terpenoid

Natural Products
Terpenes and Terpenoids constitute a large class of natural products
built up from isoprene units.
Terpenes are technically only hydrocarbons, while terpenoids are
oxygenated.

Isoprene Rule: The basic molecular formulae of terpenes are

multiples of (C5H8)n where n is the number of linked isoprene units.

Isoprene is a branched, not linear, five carbon unit.

Isoprene IsopreneUnit
 Terpene and Terpenoid
Natural Products
Classes of Terpenes
Monoterpenes are made from two isoprene units, so are C 10.
Sesquiterpenes are made from three isoprene units, so are C 15.
Diterpenes are made from four isoprene units, so are C20.
Triterpenes are made from six isoprene units, so are C30.
Tetraterpenes are made from eight isoprene units, so are C40.

Steroids are terpene derived, but carbons are rearranged or even

removed during biosynthesis, so the isoprene units may not be
recognizable.
 Monoterpenes

O O

OH
OH

Geraniol (-)-Menthol R-(+)-Carvone S-(-)-Carvone R-(+)-Limonene S-(-)-Limonene

Rose Oil Peppermint Oil Caroway Oil Spearmint Oil Orange Oil Pine Oil smell

COOH O
H
O O
Chrysanthemic Acid Nepetalactone Camphor β−Πινε νε Χαρε νε
Catnip Oil

All C10 molecules

Sesquiterpenes

OH
Farnesol Caryophyllene
Lily of the Valley Oil Clove Oil

Zingiberene
Vetivazulene Ginger Oil

All C15 molecules

 Diterpenes
OH

OH
H
OH
H H OH
HOOC OH O
Abietic Acid Crotomachlin Sarcotol

OH

Retinol
Vitamin A

All C20 molecules

Triterpenes / Tetraterpenes

Squalene
Shark liver oil
H

H
C30 molecules

HO
H Lanosterol

Lycopene - Tomato pigment

C40 molecule
Terpenes and the Isoprene Rule

Geraniol

OH OH

Carvone

O O
Terpenes and the Isoprene Rule
Vetivasulene

Caryophyllene

NOT
Terpenes and the Isoprene Rule

OH
O COOH

O OH
H
OH
Nepetalactone Chrysanthemic Acid Crotomachlin

Practice OH

Problems:
H
OH
O HOOC H
O
Camphor Sarcotol Abietic Acid

HO O
OH

Taxane Alcohol HO
H O
HO OH OH
 Steroids
H O

H
H
H
H
H H
H H
HO
HO
Cholesterol Pregnenolone

OH O OH

H H H

H H H H H H
HO O O
5-Androstenediol 4-Androstenedione Testosterone

O OH OH

H H H OH

H H H H H H
HO HO HO
Estrone Estradiol Estriol
 Terpene Biosynthesis
O O
O O O
O
Co-Enzyme A HO S-Co-A
S-Co-A S-Co-A
OH Thiolase acetoacetyl-CoA
acetyl-CoA

O
O OH O O OH
S-Co-A NADPH
HO S-Co-A HO OH
H2O HMG-CoA Reductase
3-hydroxy-3-methylglutaryl-CoA mevalonic acid
HMG-CoA Synthase

O O-PO3H2 -CO2
ATP O O
H mevalonate 5-pyrophosphate
mevalonate kinase O O P O P OH
decarboxylase
OH OH

O O O O
O P O P OH isopentenyl pyrophosphate O P O P OH
OH OH isomerase OH OH
isopentenyl pyrophosphate 3,3-dimethylallyl pyrophosphate
 Terpene Biosynthesis

O P P O P P O P P
H

O P P
Geranyl pyrophosphate

O P P O P P
O P P
Farnesyl pyrophosphate
 Terpene Biosynthesis

O P P Ισοµ ε ρασε O P P

−Η+ +Η2 Ο

OH
R-Limonene α−Τε ρπε νολ
Αλκε νε ατταχκσ
χατιον

−Η+ −Η+

α−Πινε νε β−Πινε νε
 Terpene Biosynthesis

+H2O

HO

O
P P

+H+ -H+
HO H
HO HO H
Eudesmol
Terpene Biosynthesis

OH OH OH

+H+

OH OH

H
-H+

H H Manool
 Cholesterol Biosynthesis
O
OH OPP
OH
Acetic Acid Prenyl Alcohol Farnesyl pyrophosphate

+ 2 e-

Squalene Oxide + H+
Squalene
O Squalene Cyclase

H
+
H H
H +

H H
HO HO
OH+ H H
Protosterol Cation
Cholesterol Biosynthesis
H
+
H H
H +

H H
HO HO
H H
Protosterol Cation

H
H H

+ H H H

+ +
H H H
HO HO
H H HO
H

Lanosterol
HO
H
 Cholesterol Biosynthesis
H H

H H
- CH3
- CH3 - CH3
H
HO HO
Lanosterol

H
H
H
H
H
H
H H
H H
HO H H
Zymosterol HO
HO Desmosterol

H NADPH

H
H

H H
HO Cholesterol
 Steroid Biosynthesis
H O

H
H H
H
Two Steps
H H
H H
HO Pregnenolone
HO Cholesterol

Two Steps Four Steps

O
O
H Two Steps
H
H H
HO Dehydroepiandrosterone H H
O
4-Androstenedione
One Step
One Step
OH
OH
OH
H H
H
H H Two Steps Aromatase
H H
HO H H
O
HO
5-Androstenediol Testosterone Estradiol
End