Synthesis of Ryanodol

Structure of Ryanodol

C19H30O8

Principal investigatorPierre Deslongchamps
Publication year1979
Synthesis typeTotal
Number of steps 41 (3 parts)
References
Part 1 of 3
intermediate structure
H2, PtO2
Et2O
intermediate structure
  1. O3
  2. H2
  3. Pd/C
EtOAc
intermediate structure
(CH2OH)2, TsOH
PhH
70% (3 steps)
intermediate structure
LiH, VinylLi
THF
intermediate structure
Part 2 of 3
intermediate structure
MeOCHCl2, TiCl4
CH2Cl2
intermediate structure
BBr3
CH2Cl2
80% (2 steps)
intermediate structure
BrCH2COBr
Pyr
intermediate structure
Na2CO3
THF
Reflux, , 80% (2 steps)
intermediate structure
NH2NH2, KOH
Ethylene Glycol
80%
intermediate structure
NBS, NaOH
MeCN, H2O
95%
intermediate structure
Part 3 of 3
intermediate structure + intermediate structure
PhH
Reflux, 60 min, 100%
"Mixture of isomers."
intermediate structure
NaOH
THF, H2O
RT
See the Aldol Addition
"Mixture of isomers."
intermediate structure
AcOH
H2O
75 °C, 2 h
"Mixture of isomers."
intermediate structure
NaOH
THF
RT
See the Aldol Addition
intermediate structure
Phosgene, Pyr
PhH
27% (4 steps)
intermediate structure
HC(OMe)3, TsOH
MeOH
intermediate structure
AcOOH, NaOAc
AcOH, H2O
RT to 80 °C, 16 h, 85% (2 steps)
intermediate structure
WCl6, n-BuLi
THF
-78 °C, , 80%
intermediate structure
  1. O3
  2. TsOH
  3. Me2S
EtOAc
90%
See the Aldol Addition
intermediate structure
  1. i-Pr2NLi
  2. Et3B
  3. MeI
THF
-78 to -25 °C, 3 h, 70%
intermediate structure
NaBH4
THF, MeOH
0 °C, , 95%
intermediate structure
  1. NaH
  2. MeOCH2Cl
THF
80%
intermediate structure
LiAlH4
THF
95%
intermediate structure
CrO3.2Pyr
CH2Cl2
-45 to -22 °C, 60 min, 76%
intermediate structure
MsCl
Pyr
0 °C, 60 min, 89%
intermediate structure
Dimsyl lithium
DMSO
RT, 30 min
intermediate structure
HBF4
H2O
0 °C, 3 h, 97% (2 steps)
intermediate structure
AcOOH, Na2HPO4
DCE
4 °C, 15 h
intermediate structure
NaOH
DME, H2O
RT, 5.5 h, 77% (2 steps)
intermediate structure
p-NO2BzCl
Pyr
0 °C, 25 min, 95%
intermediate structure
CrO3.2Pyr
CH2Cl2
RT, , 78%
intermediate structure
LiBH4
THF
-30 to -20 °C, 90 min, 73%
intermediate structure
Ac2O
Pyr
RT, , 100%
intermediate structure
TsOH
PhH
Reflux
intermediate structure
  1. O3
  2. Me2S
CH2Cl2
intermediate structure
NaOAc
Ac2O
100 °C, 15 h
intermediate structure
DBN
PhH
75 °C, 2.5 h, 50% (4 steps)
intermediate structure
NaBH4
THF
0 °C, 2 h, 90%
intermediate structure
NaOH
H2O
RT, 24 h
intermediate structure + intermediate structure
AcOOH, Na2HPO4
DCE
RT
intermediate structure + intermediate structure
Li
NH3
60% (3 steps)
intermediate structure