Synthesis of Asteltoxin

Structure of Asteltoxin

C23H30O7

Principal investigator	Stuart L. Schreiber
Publication year	1984
Synthesis type	Total
Number of steps	20 (3 parts)
References	J. Am. Chem. Soc. 1984, 106, 4186. J. Am. Chem. Soc. 1983, 104, 6723.

Part 1 of 3

intermediate structure

+

intermediate structure

hν

PhH

RT, 6 h, 63%

See the Paterno-Büchi Reaction

intermediate structure

mCPBA, NaHCO3

CH2Cl2

80%

See the Prilezhaev Reaction

intermediate structure

HCl

H2O, THF

intermediate structure

Me2NNH2, MgSO4

CH2Cl2

72% (2 steps)

intermediate structure

EtMgBr

THF

RT, 48 h

See the Grignard Reaction

intermediate structure

Camphorsulfonic acid, CuSO4

Acetone

55% (2 steps)

intermediate structure

Li

Et2O, NH3

98%

See the Birch Reduction

intermediate structure

o-NO2PhSeCN, n-Bu3P

THF

intermediate structure

H2O2

H2O, THF

81% (2 steps)

See the Grieco Dehydration

intermediate structure

O3 , NaHCO3
Me2S

CH2Cl2, MeOH

-78 °C to RT

intermediate structure

+

intermediate structure

n-BuLi

THF

-78 °C, 40 min, 67% (2 steps)

"Also isolated was the C1-epimer (21 % yield)."

intermediate structure

Camphorsulfonic acid

CH2Cl2

RT, 8 h

intermediate structure

(CF3CO)2O, NaOAc, 2,6-Lutidine

Ac2O

RT, 60 min

See the Pummerer Rearrangement

intermediate structure

CaCO3, HgCl2

H2O, MeCN

RT, 2 h, 60% (2 steps)

intermediate structure

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Part 2 of 3

intermediate structure

K2CO3, MeI

Acetone

intermediate structure

NaNH2, CO2

Et2O, NH3

intermediate structure

CDI

THF

intermediate structure

K2CO3, Me2SO4

Acetone

intermediate structure

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Part 3 of 3

intermediate structure

+

intermediate structure

i-Pr2NLi, HMPA

THF

-78 °C, 20 min, 80%

See the Aldol Addition

intermediate structure

DMAP, Et3N, TsCl

CH2Cl2

RT, 12 h, 82%

intermediate structure

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