Synthesis of Dysinosin A

C26H44N6O10S
Principal investigator | Stephen Hanessian |
---|---|
Publication year | 2002 |
Synthesis type | Total |
Number of steps | 32 (3 parts) |
References |
Part 1 of 3
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NaH2PO4,
NaClO2,
2-Methyl-2-butene
t-BuOH
0 °C to RT, ON, 75% (2 steps)
See the Pinnick-Lindgren Oxidation


HOBt,
EDC
CH2Cl2
0 °C to RT, ON, 95%

H2,
Pd/C
1 atm
MeOH
RT, 5 h, 99%

Part 2 of 3

Imidazole,
TBDPSCl
DMF
0 °C to RT, ON, 90%

i-Bu2AlH
CH2Cl2
-78 °C, 20 min, 90%

AllylNH2,
MsCl
CH2Cl2, Et3N
0 °C to RT, ON, 84%

Boc2O,
Et3N
CH2Cl2
RT, 60 min, 100%


n-Bu4N+ F-
THF
0 °C to RT, 70 min, 92%


CF3CO2H
CH2Cl2
RT, 4 h


CHCl3
RT, ON, 86% (2 steps)


Part 3 of 3
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- TMS2NLi
- AllylBr
THF
-78 °C, 92%

CF3CO2H
CH2Cl2
RT, 20 min, 83%

PhMe
Reflux, 90 min

- TMS2NLi
- ClCO2Bn
THF
-78 °C, 2 h

LiBHEt3
THF
-78 °C, 90 min

Ac2O,
DMAP
CH2Cl2
RT

BF3.OEt2,
AllylSnBu3
PhMe
-78 °C, 5 h, 70% (5 steps)
"Also isolated was the C5-epimer (13 % yield)."



CF3CO2H
H2O, THF
RT, ON, 75-79% (2 steps)

MeOCH2Cl,
i-Pr2NEt
CH2Cl2
RT, 18 h, 98%

H2,
Pd(OH)2
1 atm
MeOH
RT, 3 h, 95%


i-Pr2NEt,
BOP-Cl
MeCN
0 °C to RT, 25 h, 83%

LiOH
MeOH, THF
RT, ON, 97%


HOBt,
EDC
CH2Cl2
RT, 24 h, 95%

n-Bu4N+ F-
THF
RT, 4 h, 97%

Pyr.SO3,
n-Bu2SnO
CH2Cl2
RT, 6 h

CF3CO2H
CH2Cl2
RT, 6 h, 35% (2 steps)
