Opsenica

n-Bu3P
O
O Ph CH2Cl2, s.t.
CF3 + CO2Me
88%
E/Z=11/1

O NH

O Ph CH2Cl2, s.t.
CO2Me +
89%
A/B=9/1
A B

O
O O

H CsOH·H2O
N
Cl dioksan, s.t.
O 80%

O
 Opsenica
Pirol
OH
O 2C Lipitor (Pfizer)
OH Contempory Drug Synthesis
F Wiley, 2004
N
snižava nivo holesterola u krvi
(statin)
NH od 1997. godine 125 milijardi $
O

Paal-Knorr EtO OEt

OEt
F F
O H2N OEt N

O NH
CONHPh O

Et

N N CO2Et
H H
 Opsenica
Furan

O
Rozefuran
komponenta ružinog ulja
Rosa damascena

Br
?
O O

CO2Et

+
O

1) m-CPBA, CH2Cl2, 0 °C
OH 2) CSA, 0 °C
O O
(CH2)5OBn
EtO
HO

O
SO 3H CSA
 Opsenica
Tiofen

CO2Et
+
t-BuO2C S NH2

1) S8, piperidin
O 55 °C  65 °C
O 2) Ac2O, 
+
CN
 Opsenica

S NBS S NBS, K2CO3 S Br

Br
DMF, s.t. DMF, s.t.
O O O
N 80% N 87% N
NH NH NH
N N N

NH2

S CO2Me

S
N S
SMe
CN NH2
LDA, THF, 0 °C
Ph
S S
Br Ph Me2N
THF, 0 °C  s.t.

S
N I2, K2CO3
CO2Et
SMe CH2Cl2, s.t.
LDA, THF, 0 °C
62%

Br Ph
OMe
THF, 0 °C  s.t.
 Opsenica
Indol

NO2 (CO2Et)2, KOEt

DMF, 100 °C
O
N

AcOH, H2O, 
+
NH2 HO
N O

MeO
+ CO2Et
N N
H
 Opsenica

HSCH2CO2Me CF3
NaH, DMSO, s.t.
CO2Me
S

LiN(SiMe3)2, CsF
CN CPME, 110 °C O
+ CPME:
F

Ph CN
O 1) LDA, THF, s.t
2) 4-Tol-CN, PhH, s.t.
4-Tol-CN:
N
C25H20N2

1H i 13C NMR na stranama 2 i 3

 Opsenica
Ph CN
O 1) LDA, THF, s.t
2) 4-Tol-CN, PhH, s.t.
4-Tol-CN:
N
C25H20N2
 Opsenica
Ph CN
O 1) LDA, THF, s.t
2) 4-Tol-CN, PhH, s.t.
4-Tol-CN:
N
C25H20N2
 Opsenica

N N

Stenuzin
Stenus comma
 Opsenica
Hinolin
H N
N

Cl N J. Am. Chem. Soc., 1946, 68, 113

Hlorokin
OEt O
AcOH O
O O 40 °C 250 °C
+
EtO CO2Et 80% 80%
Cl NH2 Cl N Cl N CO2Et
H CO2Et H
C12H10ClNO3

1) KOH, H2O, EtOH

2) 270 oC

N
H N H2N
N Cl O
180 °C POCl3, 

Cl N 90% Cl N 90% Cl N
H
 Opsenica
Hinolin & “miscellaneous”
HO
N CF3
H ? NH2 -
OTf
NaBH4, MeOH
100 oC
+
N CF3 N N
CF3 N N
H H
Meflokin
O TBAI (10 mol%)
ClCH2CH2Cl, 80 °C
Ph

NH2 99% N Ph
wet DCE was used

CO2Et
1) BF3·OEt, CH3CN, 0 oC  s.t.
OH
2) DBU, CH3CN, 0 oC  s.t. EtO 2C
Ph
+ Ph
N 90% Ph N Ph
Ts Ph
Ts
Ph

HSCH2CO2Me NaOH, H2O PhNHNH2

o
CO2Me NaOMe, MeOH,  DMSO, 140 C AcOH, 120 oC
Ph
Br

C12H10O3S C10H8OS
J. Am. Chem. Soc. 2020, 142, 1206

1) NaHMDS, THF, -78 oC

O 2) A, THF, -78 oC DBU, PhMe, 150 oC, W

OMe 71% 60%

A: CHO B C
N
Boc C

DBU, PhMe
150 oC, W
B C
60%

C
 1) NaOAc, 1,4-dioxane, 25 oC A
2) H2SO4, 60 oC

68%

O C12H8F3NO2
CN O
+ Br
F3C

B
Na2CO3, 1,4-dioksan, 80 oC

83%

C12H8F3NO2

A B