Synthesis of Dysinosin A

Structure of Dysinosin A

C26H44N6O10S

Principal investigatorStephen Hanessian
Publication year2002
Synthesis typeTotal
Number of steps 32 (3 parts)
References
Part 1 of 3
intermediate structure
Pb(OAc)4, Na2CO3
CH2Cl2
0 °C to RT, 2.5 h
intermediate structure
NaClO2, 2-Methyl-2-butene, NaH2PO4
t-BuOH
0 °C to RT, ON, 75% (2 steps)
intermediate structure + intermediate structure
EDC, HOBt
CH2Cl2
0 °C to RT, ON, 95%
intermediate structure
H2, Pd/C
MeOH
RT, 5 h, 99%
intermediate structure
Part 2 of 3
intermediate structure
TBDPSCl, Imidazole
DMF
0 °C to RT, ON, 90%
intermediate structure
i-Bu2AlH
CH2Cl2
-78 °C, 20 min, 90%
intermediate structure
MsCl, AllylNH2
CH2Cl2, Et3N
0 °C to RT, ON, 84%
intermediate structure
Boc2O, Et3N
CH2Cl2
RT, 60 min, 100%
intermediate structure
Grubbs catalyst (1st gen.)
CH2Cl2
RT, ON, 90%
intermediate structure
n-Bu4N+ F-
THF
0 °C to RT, 70 min, 92%
intermediate structure
(PhO)2P(O)N3, DEAD, Ph3P
THF
0 °C to RT, 40 min, 82%
intermediate structure
CF3CO2H
CH2Cl2
RT, 4 h
intermediate structure
CHCl3
RT, ON, 86% (2 steps)
intermediate structure
Ph3P, AcOH
THF, H2O
60 °C, 60 min, 72%
intermediate structure
Part 3 of 3
intermediate structure
  1. TMS2NLi
  2. AllylBr
THF
-78 °C, , 92%
intermediate structure
CF3CO2H
CH2Cl2
RT, 20 min, 83%
intermediate structure
PhMe
Reflux, 90 min
intermediate structure
  1. TMS2NLi
  2. ClCO2Bn
THF
-78 °C, 2 h
intermediate structure
LiBHEt3
THF
-78 °C, 90 min
intermediate structure
Ac2O, DMAP
CH2Cl2
RT
intermediate structure
BF3.OEt2, AllylSnBu3
PhMe
-78 °C, 5 h, 70% (5 steps)
"Also isolated was the C5-epimer (13 % yield)."
intermediate structure
Grubbs catalyst (1st gen.)
CH2Cl2
RT, , 99%
intermediate structure
mCPBA
CH2Cl2
RT, 2 h
intermediate structure
CF3CO2H
THF, H2O
RT, ON, 75-79% (2 steps)
intermediate structure
MeOCH2Cl, i-Pr2NEt
CH2Cl2
RT, 18 h, 98%
intermediate structure
H2, Pd(OH)2
MeOH
RT, 3 h, 95%
intermediate structure + intermediate structure
BOP-Cl, i-Pr2NEt
MeCN
0 °C to RT, 25 h, 83%
intermediate structure
LiOH
THF, MeOH
RT, ON, 97%
intermediate structure + intermediate structure
EDC, HOBt
CH2Cl2
RT, 24 h, 95%
intermediate structure
n-Bu4N+ F-
THF
RT, 4 h, 97%
intermediate structure
Pyr.SO3, n-Bu2SnO
CH2Cl2
RT, 6 h
intermediate structure
CF3CO2H
CH2Cl2
RT, 6 h, 35% (2 steps)
intermediate structure