Synthesis of Tunicamycin V

C38H62N4O16
Principal investigator | Andrew G. Myers |
---|---|
Publication year | 1993 |
Synthesis type | Total |
Number of steps | 28 (5 parts) |
References |
Part 1 of 5

KF.2H2O
MeOH
RT, 6.5 h, 100%

K2CO3,
Cl3CCN
CH2Cl2
RT, 24 h, 64%

Part 2 of 5


i-Pr2NEt,
BnOCH2Cl
CH2Cl2
Reflux, 15 h, 89%

PhSeH,
Et3N
0 to 60 °C, 2.5 h, 98%

Phthaloyl Chloride,
Et3N,
DBU
CH2Cl2, PhMe
0 to 100 °C, 100 min, 86%

PhSeH,
Et3N
DME
90 °C, 10 h, 95%

Et3N.3HF
MeCN
RT, 6 h, 97%

Part 3 of 5
+


TfOH
4A MS
PhMe
-20 °C, 24 h, 77%

NH2NH2.H2O
EtOH
100 °C, 12 h, 87%

ClCO2Bn
Pyr
0 °C, 30 min, 91%

PhSeH
Et3N
55 °C, 12 h, 91%

Ac2O
Pyr
60 °C, 2.5 h, 91%

mCPBA
CCl4
-15 to 0 °C, 50 min, 88%

K2CO3,
NaOH
RT, 2 h, 92%

Part 4 of 5

DMAP,
Et3N,
TMSCl
CH2Cl2
RT, 2 h
"DMT = Dimethoxytrityl"

DMAP,
Boc2O
Pyr
RT, 12 h

KF.2H2O
MeOH
RT, 3 h, 79% (3 steps)

ClCO2Allyl
Pyr
-20 to RT, 35 min, 87%

PhSO3H
CHCl3
RT, 2 min, 76%


Part 5 of 5
+


- PhSeH
- Me2SiCl2
PhMe, Pyr
RT, 6 h, 81%

Pd(PPh3)2Cl2,
n-Bu3SnH
CH2Cl2, H2O
RT, 6 min, 85%

Et3B,
n-Bu3SnH
0 °C, 2 h

KF.2H2O
MeOH
RT, 2 h, 60% (2 steps)

Pd,
HCO2H
MeOH
RT to 40 °C, 6.5 h

HF
H2O, MeCN, MeOH
RT, 2 h


DCC
CH2Cl2, MeOH
RT, 2 d, 83% (3 steps)
