Synthesis of Stigmatellin A

Structure of Stigmatellin A

C30H42O7

Principal investigatorDieter Enders
Publication year2000
Synthesis typeTotal
Number of steps 22 (4 parts)
References
Part 1 of 4
intermediate structure
P2O5, H3PO4
EtCO2H
70 °C, 60 min, 73%
intermediate structure
mCPBA, CF3CO2H
CH2Cl2
5 °C, 16 h, 87%
intermediate structure
HCl
MeOH, H2O
Reflux, 2 h, 99%
intermediate structure
MeOCH2Cl, i-Pr2NEt
CH2Cl2
0 °C to RT, ON, 98%
intermediate structure
Part 2 of 4
intermediate structure
4-Methoxyphenol, DEAD, Ph3P
CH2Cl2
0 °C to RT, 3 d, 95%
intermediate structure
NaI
Acetone
Reflux, 5 d, 83%
intermediate structure + intermediate structure
i-Pr2NLi
Et2O
-100 °C to RT, ON, 80%
intermediate structure
MMPP
MeOH, Buffer (pH = 7)
-15 °C, 15 min, 87%
intermediate structure + intermediate structure
TiCl4, i-Pr2NEt
CH2Cl2
-78 °C to RT, 3.5 h, 64%
See the Aldol Addition
intermediate structure
Me4N+ BH(OAc)3-, AcOH
MeCN
-40 to -20 °C, 3 d, 99%
intermediate structure
  1. KH
  2. 18-Crown-6
  3. MeI
THF
0 °C to RT, 2 d, 77%
intermediate structure
(NH4)2Ce(NO3)6
MeCN, H2O
0 °C, 6 min, 90%
intermediate structure
H2Cr2O7.2Pyr
DMF
RT, ON, 100%
intermediate structure
Part 3 of 4
intermediate structure + intermediate structure
NaH
THF
-78 °C to RT, ON, 71%
intermediate structure
i-Bu2AlH
Et2O
-78 °C, 60 min, 99%
intermediate structure
PBr3
Et2O
0 °C, ON, 93%
intermediate structure
P(OEt)3
160 °C, ON, 63%
intermediate structure
Part 4 of 4
intermediate structure + intermediate structure
t-BuCOCl, i-Pr2NEt, DMAP
CH2Cl2
RT, 3.5 h, 57%
intermediate structure
NaOMe
MeOH
Reflux, 2 h, 75%
intermediate structure
H2, Pd/C
MeOH
RT, 6 min, 74%
intermediate structure
(COCl)2, DMSO, i-Pr2NEt
CH2Cl2
-78 °C to RT, 40 min
See the Swern Oxidation
intermediate structure + intermediate structure
i-Pr2NLi
THF
-78 °C to RT, ON, 77% (2 steps)
intermediate structure