OLEH:
FENIL PROPANOID
CO2H
C C
C
HO OH
HO
Turunan Sinamat
CO2H CO2H
CO2H CO2H
1
6 2
5 3
4 OH HO OH
OH OH OH
Turunan Kumarin
8 1
O O HO O O HO O O
7
2
6 3
5 4 HO
Kumarin Umbeliferon Eskulatin
Turunan Alilfenol
H3CO
OCH3
O O
OH OH O O
Turunan Propenilfenol
- CO2
OH
[O] [O]
- CO2 - NH3
+ R1 R2
OH H
OH OH OH
Tirosin Asam -kuramat
6
3
5 4
Kumarin
(benzopiran-2-on)
H
Biosintesis Kumarin H
O
OH O
H C O -H2O
H H
Asam sinamat cisoid transoid
O O HO O O HO O O
[O]
RO
H3CO O O
O O O O O O
H3CO
O O O O O O HO O O H3CO O O
HO
Psoralen OCH3
OH
Bergapten Kumestrol
Dalbergin
Biogenesa Benzofuran
-H2O
O O
O O O
H OH
H+
O O-
2H+
-H2O
O O O
O OH
5 5
4 2 4 2
3 3
R R
Subtituen cincin
Chavikol OH ……...
Estragol OCH3 Anotol
Eugenol OCH3 OH Isoeugenol
Safrol -O-CH2-O- OH Isosafrol
Elemisin OCH3 OCH3 OCH3 Isoelemisin
Miristin -O-CH2-O- OCH3 Isomiristin
Apinol OCH3 -O-CH2-O- OCH3 Isoapiol
Biosintesa Alilfenol dan propenilfenol
CO2H CH2X CH2
[H] -X H-
R R R R
Asam sinamat Karbokation antara
R R
Propenilfenol Alifenol
POLIKETIDA
Turunan Aslifroroglusinol
O O OH
O O OH
(C5)
C C
H3 C C CH2
OH2
4 × C2 C CH2
C HO O
HO HO OH
H2
Turunan Kromon
O OH O OH HO O
O
5× C2 O
(C5)
O O OH O OH O
5-hidroksi-2-metil-kromon Pucenin
Turunan benzokuinon
O O O
HO CH3 HO CH3
O OH
O H3CO H3CO OH
O O O
Fumigatin Spinulosin
Turunan naftakuinon
O O
O
m
6(7)xC2 O O O
OH O
O O O OH O OH O
Plumbagin Javanisin
(m=0) (m=1)
Turunan antrakuinon
O O O O OH O OH OH O OH
CO2H CO2H
3 x C2 O O O OH
O HO HO
O O
Endokrosin Emodin
Biosintesa Poliketida
CO2H
CO2
CH3CO2H CH3CO SCoA CH2 CO SCoA
asetil koenzim-A malonil koenzim-A
CH3
C O
S CoA
O O O CO2H O O
CH2CO SCoA
H3C C CH2 C CH2 C SCoA CH3 C CH2 C SCoA
O O O O
(a)
O O HO OH
asam orselinat
O O O O R=CH3
R=CH3(-COCH2)n- ; n= 0, 1, 2,
R C CH2 C CH2 C CH2 C OH
O O O OH
(b)
R R
Kondensasi aldol sering pula terjadi antara gugus metilena dan gugu karbonil yang terletak di bagian tengah
dari rantai poliasetil
O O O O OH O OH O
OH OH
O O O
O CH3 HO CH3
Oktasetil
OH O OH OH O OH O
OH
HO CH3 HO CH3
O O
Emodin Endokrosin
O (c) O
R OO O R O O
O O O O -piron
HH
R C CH2C CH2C CH2C OH O O OH O
O
O
O O OO R O OO R
HH
O
R OO OH OH O
HH
O
HO O R
Kromon
O
O
R O OH R CH C CH2n ; n = 0, 1, 2, ...
-piron
Dari siklinisasi, laktonisasi (c) merupakan satu-satunya proses yang terjadi
O O OH
OO OO
R O R O R O O
H HH
O
R = CH3 atau CH3CCH2-
O O O OCH3 O OCH3
O O
O O O OH3C O
O
Cl H3C
Griseofulvin
Stabilotas terakhir senyawa yang dihasilkan,
O O HO O
CH3
H3C
O
HO
[H]
H3C
CH3
Klavatrol
OH O OH O
H3C
HO HO
ALKALOID
O
o
CO2H
NCH3 OCCHC6H5
CH
NH2
N CH2OH
NH2
CH3
Omitin Higrin Higsiamin
O
CO2H O
NH
CH
NH2 NH2 N
H
Lisin Isopelitierin Pseudopeletierin
OCH3
Fenilalanin : R1=R2=H Hordenin Hordenin
Tirosin : R1=H, R2=OH
Dihidoroksi Fenilalanin : R1=R2=OH
H3CO
O
N
N+
H3CO O
OCH3
OCH3
OCH3
OCH3
Laudanosin Berberin
3. Alkaloid Aromatik Indol
OPO3H2
HO
HO
CO2H
CH
NH2
N NH2
N NH2
N
H
H
H
Triptofan Serotonin Psilosibin
HO2C CH3
N
HO
N
HO
NH N
Asam lisergat
Kuinin *)
*) Kuinin mempunyai cin-cin Kuinolin (bukan indol),
tetapi secara biogenetik bertalian dengan indol
Biosintesis Alkaloid
Prinsip: Kondensasi Mannich
O
-CO2
-NH2 R O- H OH
H
Asam amino l +
Aldehid R C N R R C °°
N R R
-CO2 C N R
H
H R1 H R1 R1
°° H Imina : R1 =H
N
H C C Imonium : R1 =alkil
R
Amina
Primer : R1 = H O ll
H Enol/fenol
Sekunderr : R1 = alkil
I : Pembuntukan C-N R
II : Pembentukan C-C
Alkaloid C C N R
R1
O H
Reaksi-reaksi sekunder
Biosintesa Alkaloid Alisiklik
-CO2 [o]
Mannich
CO2H C O
H2N H2N H2N H2N H2 N
Ornitin N
Imina
CO2H O
+ O
+
CH2 CO CH3 Mannich -CO2
N N N
CH3
CH3 CO2H CH3
Garam imonium Higrin
[o] Mannich
NCH3 O +NCH3 O NCH3 O
NCH3 OCCH2C6H5
CH2OH
Hiosiamin
Biosintesa Turunan Lisin
CO2H
NH2 NCH3 O
Isopeletierin
NH2
NCH3 O
Pseudopeletierin
Biosintesa Nikotin dan Anabasin
CO2H
O
C N
Asam nikotinat
H2N H2N CO2H H2N H2N H
HN N
CH3
N
Nikotin
CO2H
N N
Asam nikotinat H
H2N H 2N CO2H
N N
Lisin Nikotin
NH2 N(CH3)2
NH2 OH OH
OH
Tirosin Hordenin
C2OH H3CO
N(CH3)2
HO
NH2 OH
OH OCH3
3,4-Dihidroksifenilalanin Meskalin
Hubungan Biogenetik Alkaloid Turunan 1-Benzilisokuinolin
C2OH HO HO
CO2 CHO
NH2
NH2 OH OH
OH 3,4-Dihidroksitiramin
Tirosin
HO H3CO
NH N
OH CH3
H3CO
OCH3
OH
Norllaudanosin Laudanosin
OH OCH3
H3CO
A B
N
HO CH3
OH
C
Retikulin
OCH3
OCH3 OCH3 HO
C C C
OH OH
O
B N B N B N
CH3 A CH3 A CH3
A
OCH3 OCH3 O
Morfin
OH O
Salutaridin
Biosintesa Beberapa Alkaloid Indol
CO2H OH
NH2 NH2
N N
H H
HPo3H2 Serotonin
Triptofan OH
N(CH3)2
N
H
PSILOSIBIN
H2N HOH2C
NHCH3
CO2H
NH2 N
N H
H
N
Triptofan H
Chanoclavin
NCH3
CO2H
NCH3
N
H
N
H
Groklavin Asam Lisergat
CHO
O-Glukosa
OPP
O
O CO2CH3
secolonganin
longanin
CO2H
NH2
N
H
Triptofan
N NH
N N
H H
O-glukosa
O O
CO2CH3 CO2CH3
Serpentin Striktosidin
FLAVANOID
Kerangka dasar karbon
C6 : Cincin benzen
C6-C3-C6 C3 : rantai propan
C3
C4 C2
C2 C1
C3 C1
C2
C1
Isoflavanoid Neoflavanoid
Flavanoid (1,2-diarilpropan)
(1,3-diarilpropan) 1,1-diarilpropan
HO O O
H 3CO
R1
O
O R1
O
OH
Deidzen : R=H Pterokarpin OH
Genisten : R=H O Kumestrol : R1=R3=H; R2=OH
Modelolakton : R1=R3= OH;R2=OCH3
4-arilkumarin Dalbergion
Rotenoid
H3CO O O H3CO O
R
HO
O
O O
O
R1
1
H
O 2
O O
OH
O O OH OH
Dihidrocalkon calkon Flavan Katekin Leukoantosianidin
O
O O O
O OH OH
O O O
Flavanon Flavanonol Flavon Flavonol
O O
OH
Garam Flavilum Anlosianidin
OH O OH O
Floretin Kaemferol
Biosintesa Flavanoid
Kombinasi dua jalur biosintesa
R
R
R
3AeCnA HO
HO
CuA-S
O O O O
O
O
R R
HO O HO OH
OH O OH O
Flavanon Calkon
HO HO OH
O
OH
OH O OH O HO
Calkon O
Flavanon
o
OH
OH OH-
OH O
HO H Flavanonol
O OH
a
b c
HO O
H
HO
OH O b
C OH OH
H OH O
a
c Flavanol
OH Auron
HO OH Katecin
O
HO Anntosiannidin
O
OH O
OH OH O
Isoflavon
Flavon
Variasi Struktur Flavonoid
OH OH
OH
H3CO OH RO O
H3CO O
O O
OH O
Bavacalkon Bavachin : R=H
Bavachinin : R=OCH3 Cyelomulberin
OH OH OH
glu
HO OH O O HO O
OH OH culg OH
OH O OH O OH O
Muresin Deguelin 6,8-Bis(C-glucosil)-apigenin
OH
HO O
OH O
HO
Cryptomerin
OH O
Sifat-Sifat Flavonoid
B O O
O
O- O O-
1. Berflouresensi Sinamoil
Benzoil
2. max : 240-270 nm (Benzoil)
320-380 nm (Sinamoil)
OH OH
HO O HO O
[H+]
OH O + OH OH
H
Flavon Garam Flavinium
OH OH
OH
HO O HO O
HO O
[LAH] [H+]
OH OH
OH
OH OH H+ OH
OH O
Antosianidin
Flavon
A [NaOH] A (a)
CO2H
O
Asetofenon OH
OH O OH O
Flavon
HO OH
HO OH
OH
O
Asam Benzoat OH O
Floroglusinol
OH
OH H
B
HO OO
HO O
OH OH OH
[KOH] A
OH HO HOH2C
OH O OH OH
OH O
O O
Asam Protokatekuat
HO OH
OH
Floroglusinol
Interkonversi Flavonoid
OH OH
HO OH HO O
O O
OH O H
H+ Flavanon
Calkon i). RONO
SeO2 ii). H2O
H2O3
OH OH OH
HO O HO O HO O
OH OH
OH O OH O
OH O
Flavon Flavonol
Flavanonol
i) H2/Ni i) H2/Ni
ii) H+
ii) H+
OH OH
HO O HO O
OH
OH OH
Sintesa Flavonoid
OH
HO O HO O
HO OH
(ArCO)2O -
O ArCo2
ArCo2 CH3 R
R
R
OH O OH O
OH O
Flavon Flavon
OH- H+
OH
H
R OO
R O
i) HCO3H
ii) H+ R OH
OH
R O
R O