Download 1 kuliah pertama CHEMISTRY OF NATURAL PRODUCT

KIMIA BAHAN ALAM
(CHEMISTRY OF NATURAL PRODUCT)
By
MASRURI, PhD
Laboratorium Kimia Organik
website: masrurichemistry.lecture.ub.ac.id
Kontrak Kuliah
Dosen: Masruri, S.Si., M.Si., PhD dan Dr. Rurini Retnowati, MS
Penilaian: UTS (40%), Tugas-1 (20%), Tugas-2 (20%), Tugas-3 (20%)
Quesioner mahasiswa: Diberikan saat UTS
Materi: (sesui dengan Buku Pedoman Pendidikan)
Pendahuluan ---sesi 1
Triterpenoid (biosintesis, isolasi dan karakterisasi) -- sesi 2-3
Poliketida (biosintesis, isolasi dan karakterisasi) – sesi 4-5
Alkaloid (biosintesis, isolasi dan karakterisasi) – sesi 6-7
UTS
Terpenoid
Fenolik
Flavonoid
Fenil propanoid
UAS
1
Format tugas : Review artikel jurnal
Tulisan harus berisi:
Pendahuluan, review hasil-hasil penelitian yang sama/sejenis dengan topik,
kesimpulan, daftar pustaka
Total kata: 10.000-15.000 kata
Penulisan daftar pustaka:
• Daftar pustaka ditulis urut berdasar urutan abjad
• Nama penulis (semua), Judul artikel, Nama jurnal (ditulis miring), Tahun
(ditulis tebal), Volume, Nomer/Issue, Halaman
Cara melakukan sitasi dalam paragraf:
• Penulis tunggal, misalnya: Arthur (2011)
• Penulis ada 2, misalnya: Masruri dan Ari (2003)
• Penulis lebih dari 2, misalnya: Kagan et al. (2013) atau Kagan dkk. (2013
Definisi
Richard J. P. Cannell, 1998, Natural Products Isolation, Humana Press Inc., New Jersey
2
Definisi
Richard J. P. Cannell, 1998, Natural Products Isolation, Humana Press Inc., New Jersey
CO2 + H2O
PRIMARY METABOLISM
hν
Photosynthesis
Glucose
SECONDARY
METABOLISM
Building Blocks
Phenylpropanoids
Flavonoids
Alkaloids
Amno Acids
Proteins
synthesis
enzymes
regulation
Nucleic
Acids
reproduction
RNA DNA
G
L
Y
C
O
L
Y
S
I
S
Carbohydrates
SECONDARY
METABOLISM
Fatty Acids
Lipids
Acetyl CoA
Citric Acid
Cycle
Acetogenins
Terpenes
Steroids
CO2 + H2O + ATP
3
Simple building blocks serve as the basis for each major
pathway of secondary metabolism:
(1)
Shikimate
Aromatics (ring - C3 chain)
(2)
Amino acids
Alkaloids, Penicillins
(N-containing)
(3)
Mevalonate
Terpenes, Steroids
(4)
Acetate
Polyketides
(aromatics, macrocycles)
(photosynthesis)
Polysaccharides
Glycosides
Nucleic Acids
phosphoenol
pyruvate
Shikimate pathway
Aromatic Compounds
Lignans
Shikimate
pyruvate
acetyl
CoA CH3COSCoA
aromatic amino acids
aliphatic amino acids
CITRIC
ACID
CYCLE
(1)
Alkaloids (2)
Peptides
Penicillins
Cyclic Peptides
CH3COSCoA
-O
2CCH2COSCoA
CH3COCH2COSCoA
CH3COSCoA
CH3COSCoA
mevalonate
Polyketides, Fatty Acids
Isoprenoids (terpenes, steroids,
(3)
carotenoids)
(4)
Prostaglandins, Macrocyclic Antibiotics
4
Glucose
hν
CH2OH (6 carbons)
O
CH2OH
O
OH
HO
CO2
OH
HO
OH
OH
OH
OH
O
OH
starch
photosynthesis
CH2OH
O
CH2OH
O
O
OH
O
OH
n
glycolysis
CHO
CH OH
CHO
CH OH
HC OH
C O
CH2OP
erythrose4-phosphate
CH2OP
CH2OH
CH2
C OP
COOH
HO
shikimic
acid
OH
COOH
anthanilic
acid
NH2
phenylpropanes
lysine
ornithine
phenylalanine
tyrosine
tryptophan
alkaloids
phosphoenol
pyruvate (PEP)
H3C C SCoA
oxaloacetate
nicotinic
acid
O
lipids
fatty acids
O
H3C C CH2 C CH2
(3 carbons)
O
COOH
OH
polyketides
acetogenins
CH2OP
acetylcoenzymeA
(2 carbons)
citric
acid
cycle
aspartic
acid
HO
CH3
mevalonic
acid
energy (ATP)
+ CO2 + H2O
NH3
glutamic acid
O
O
terpenes
steroids
carotenoids
Sesquiterpenes from Neurolaena lobata and Their Antiproliferative
and Anti-inflammatory Activities
Ildikó Lajter, Andrea Vasas, Zoltán Béni, Peter Forgo, Markus Binder, Valery Bochkov, István Zupkó, Georg Krupitza, Richard
Frisch, Brigitte Kopp, and Judit Hohmann, J. Nat. Prod., 2014, DOI: 10.1021/np400834c
5
Antiherbivore Prenylated Benzoic Acid Derivatives from Piper
kelleyi
Christopher S. Jeffrey, Michael D. Leonard, Andrea E. Glassmire, Craig D. Dodson, Lora A. Richards, Massuo J. Kato, and Lee
A. Dyer, J. Nat. Prod., 2014, 77, 1, 148–153; DOI: 10.1021/np400886s
Pyrrolizidine Alkaloids from Onosma erecta
The MeOH extract of the aerial parts of Onosma erecta afforded four new pyrrolizidine alkaloids, 7-Oacetylechinatine N-oxide (1), a viridinatine N-oxide stereoisomer (2), 7-epi-echimiplatine N-oxide (3), and
onosmerectine N-oxide (4), and two additional new natural products, the acid 2,3-dimethyl-2,3,4trihydroxypentanoic acid (5) and the acyloin 4-methyl-2-hydroxypentanone (6).
Harilaos Damianakos, Georgios Sotiroudis, and Ioanna Chinou, J. Nat. Prod., 2013, 76, 10, 1829–1835;
DOI: 10.1021/np300785g
6
1-Deoxynojirimycin
OH
OH
HO
OH
N
H
1-Deoxynojirimycin
(1,5-dideoxy-1,5-imino-D-glucitol)
White mulberry
(Morus alba)
Inhibition: Ki = 32 nM (α-D-glucosidase)
Activity: anti-diabetes, anti-HIV, ...
Applications: Tay-Sachs, Gaucher, ...
Reference: Iminosugars as Glycosidase Inhibitors: Nojirimycin and Beyond, Ed. A. E. Stütz, Wiley, 1999.
Ladybird Beetles (Coccinellidae)
O
N
H
(-)-Pinidinone
O
N
H
(+)-2-Epipinidinone
(2R,6R)/(2S,6R)-6-methyl-2-(2,-oxo-propyl)piperidine
Mealybug ladybird beetle (Cryptolaemus
Mexican bean beetle
montrouzieri)
(Epilachna varivestis)
Reports on (epi)pinidinone occurrence:
V. W. Brown, P. B. Moore: Aust. J. Chem. 1982, 35, 1255.
A. B. Attygalle, S. Ch. Xu, K. D. McCormick, J. Meinwald, C. L. Blankespoor, T. Eisner: Tetrahedron
1993, 49, 9333.
7
Coniferous Trees (Pinaceae)
O
N
H
(-)-Pinidinone
O
N
H
(+)-2-Epipinidinone
(2R,6R)/(2S,6R)-6-methyl-2-(2,-oxo-propyl)piperidine
Ponderosa pine (Pinus ponderosa)
Colorado spruce (Picea pungens)
Reports on (epi)pinidinone occurrence:
J. N. Tawara, A. Blokhin, T. A. Foderaro, F. R. Stermitz, J. Org. Chem. 1993, 58, 4813.
F. R. Stermitz, J. N. Tawara, M. Boeckl, M. Pomeroy, T. A. Foderaro, F. G. Todd, Phytochemistry
1994, 35, 951.
KC Nicolou
8
KC Nicolou
Bactericide on E. coli of triterpenoid from Indonesia
Spathodea campanulata Beauv
Masruri et al., NATURAL JURNAL, 2008, 12, 1, 22-31
9
SOME OTHER PLANT STEROIDS
H
O
H
O
H
H
H
H
HO
H
H
H
HO
H
diosgenin
sigmasterol
O
(soy beans)
(mexican yams)
O
Used by Marker to synthesize
the first birth control pills.
SYNTEX
OH
HO
H
H3C
H
digitoxigenin
H
C C
H
H
(Digitalis spp , foxglove)
OH
H
O
norethindrone
O
O
H3C
H
O
H C
H
H
H
H
HO
H
β-sitosterol
wheat germ oil, corn oil
HO
O
HO
O
CH3
sapogenin, arrow poison
H
H
O
Strophanthus spp
H3C
HO
OH
strophanthidin
O
HO
HO
OH
OH
OH
ouabain
Strophanthus spp
sapogenin, arrow poison
OH OH
10