(ISOPRENOID)
DEFINITION Terpenes:
Natural products that posses a carbon framework comprised of units of five carbon arrangement as below:
isoprenic
isoprenic
isoprenic
isoprenic
Classification of Terpenes
Based on isoprenic
1. Hemiterpenes (1 x C5)
HO 3-methylbut-2-en-1-ol
Asam isovalerat
Etil isovalerat
2. Monoterpenes (2 x C5)
OH
OH
menthol
geraniol
limonene
-Mircena
(mint)
(roses)
(orange fruit)
3. Sesquiterpenes (3 x C5)
OH farnesol
bisabolen
-(-)-Bisabolol
-Kurkumena
Zingiberene
4. Diterpenes (4 x C5)
OH
manool
Cembren
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)
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
Mellitoxin
OH CHO OH
CHO HO
OH
HO
OH
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
Monoterpenes
OPP H
Triterpenes 2x Tetraterpenes 2x
OPP geranyl-geranyl pyrophosphate (GGPP)
Diterpenes
Sesquiterpenes
Example:
OH
geraniol
-Mircena
citral
citronellal
Example:
limonene
-Terpeneol
Example:
bisabolen
Example:
Reactions of Terpenoids
HO 3-methylbut-2-en-1-ol
OH
menthol
OH
geraniol