Synthesis of Ryanodol

C19H30O8
Principal investigator | Pierre Deslongchamps |
---|---|
Publication year | 1979 |
Synthesis type | Total |
Number of steps | 41 (3 parts) |
References |
Part 1 of 3

H2,
PtO2
Et2O

- O3
- H2 , Pd/C
EtOAc

(CH2OH)2,
TsOH
PhH
70% (3 steps)

LiH,
VinylLi
THF

Part 2 of 3


BBr3
CH2Cl2
80% (2 steps)

BrCH2COBr
Pyr



NaOH,
NBS
H2O, MeCN
95%

Part 3 of 3
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AcOH
H2O
75 °C, 2 h
"Mixture of isomers."


Pyr,
Phosgene
PhH
27% (4 steps)

TsOH,
HC(OMe)3
MeOH

NaOAc,
AcOOH
AcOH, H2O
RT to 80 °C, 16 h, 85% (2 steps)
See the Baeyer-Villiger Oxidation
See the Prilezhaev Reaction

n-BuLi,
WCl6
THF
-78 °C, 80%


- i-Pr2NLi
- Et3B
- MeI
THF
-78 to -25 °C, 3 h, 70%

NaBH4
MeOH, THF
0 °C, 95%

- NaH
- MeOCH2Cl
THF
80%

LiAlH4
THF
95%


MsCl
Pyr
0 °C, 60 min, 89%


HBF4
H2O
0 °C, 3 h, 97% (2 steps)


NaOH
DME, H2O
RT, 5.5 h, 77% (2 steps)

p-NO2BzCl
Pyr
0 °C, 25 min, 95%


LiBH4
THF
-30 to -20 °C, 90 min, 73%

Ac2O
Pyr
RT, 100%

TsOH
PhH
Reflux

- O3
- Me2S
CH2Cl2

NaOAc
Ac2O
100 °C, 15 h

DBN
PhH
75 °C, 2.5 h, 50% (4 steps)

NaBH4
THF
0 °C, 2 h, 90%

NaOH
H2O
RT, 24 h




Li
NH3
60% (3 steps)
