TERPENOID

(ISOPRENOID)

DEFINITION Terpenes:
Natural products that posses a carbon framework comprised of units of five carbon arrangement as below:

isoprenic

isoprenic

isoprenic

isoprenic

commonly indicated by symbol C5

Classification of Terpenes
Based on isoprenic

1. Hemiterpenes (1 x C5)
HO 3-methylbut-2-en-1-ol

(,-dimethylallyl alcohol) Prenol

Asam isovalerat

Etil isovalerat

2. Monoterpenes (2 x C5)

OH

OH

menthol

geraniol

limonene

-Mircena

(mint)

(roses)

(orange fruit)

Sources: volatile oil (minyak atsiri)

3. Sesquiterpenes (3 x C5)

OH farnesol
bisabolen

-(-)-Bisabolol

-Kurkumena

Zingiberene

Sources: volatile oil (minyak atsiri)

Minyak atsiri terdapat pada

Bunga, daun, buah dan akar dari bermacam tumbuhan mengandung bahan yang mudah menguap dan berbau wangi cengkeh kayu manis pinaceae pinus umbelliferae ketumbar saladri adas

4. Diterpenes (4 x C5)

OH

manool

COOH pimaric acid

Cembren

Sources: pine resin

Kafestol

5. Sesterterpenes (5 x C5)

COOH

HO

gascardic acid

ophiobolin F

Gascardic acid is the first sesterterpenes that was isolated in 1965 from the secretion of an insect, Gascardia madagascariensis

6. Triterpenes (6 x C5)

OH

HO

dammarane

dammarenediol

OH

HO malabaricol

Source: damar

7. Tetraterpenes (8 x C5)

lycopene

a-carotene

B-carotene
Source: carotenoid pigment (carrots)

8. Polyterpenes (> 8 x C5) : polyisoprene

natural rubber

Frequently occur in nature, polyisoprene chains made up with more than 10 C5 units, bound tail to head Source: natural rubber

Irregular Terpenoids
O

cryptone

2-methylhept-2-en-6-one

-phellandrene

Those with a skeleton of less than ten carbon atoms (Apparent and False Monoterpenes) Those compounds are a defense substance from certain insects Cryptone and 2-methylhept-2-en-6-one: Very likely derives from the oxidative cleavage of the C2-C3 bond of an acyclic monoterpene

OH
OH

nezukone

chrysanthemic acid

fenchol

lavandulol

those compounds contain ten carbon atoms but they do not follow the isoprene rule It is more difficult to find a biogenetic explanation for the structures of above compounds

Toxic sesquiterpenes
O O R O O

O O HO O O OH

Coriaria species

R = H; Coriamyrtin R = OH; Tutin

Mellitoxin
OH CHO OH

CHO HO

OH

HO

OH

seeds from cotton plants

Gossypol

Biosynthesis of Terpenoids
Secara umum biosintesis terpenoid dengan terjadinya 3 reaksi dasar yaitu : 1. Pembentukan isopren aktif (IPP dan DMAPP) berasal dari asam asetat melalui asam mevalonat 2. Penggabungan kepala ke ekor dari 2 unit isopren akan membentuk mono-, seskui-, di-, sester- dan politerpenoid 3. Penggabungan ekor ke ekor dari unit C-15 atau C-20 menghasilkan triterpenoid (dan steroid) dan tetraterpen

Biosynthesis of Terpenoids

(IPP)

(DMAPP)

OPP
H

OPP

OPP geranyl pyrophosphate (GPP)

Monoterpenes

OPP H

Triterpenes 2x Tetraterpenes 2x
OPP geranyl-geranyl pyrophosphate (GGPP)
Diterpenes

OPP Farnesyl pyrophosphate (FPP)

OPP H

Sesquiterpenes

Other reactions on GPP, FPP and GGPP to produce terpenoids:

Hydrolysis Cyclisation Oxidation Reduction Isomerization Dehydration Decarboxylation etc

Example:
OH

geraniol

-Mircena
citral

OPP geranyl pyrophosphate (GPP)

citronellal

Example:

limonene

-Terpeneol

Example:

bisabolen

Example:

Reactions of Terpenoids

HO 3-methylbut-2-en-1-ol
OH

menthol

OH

geraniol