Asteltoxin

"Dedicated to the memory of Professor Kunio Sakan."

Part 1 of 3

hν

PhH
RT, 6 h, 63 %

See the Paterno-Büchi Reaction

mCPBA, NaHCO₃

CH₂Cl₂
80 %

See the Prilezhaev Reaction

HCl

THF, H₂O

Me₂NNH₂, MgSO₄

CH₂Cl₂
72 % (2 steps)

EtMgBr

THF
RT, 48 h

See the Grignard Reaction

CuSO₄, Camphorsulfonic acid

Acetone
55 % (2 steps)

NH₃, Et₂O
98 %

See the Birch Reduction

o-NO₂PhSeCN, n-Bu₃P

THF

H₂O₂

THF, H₂O
81 % (2 steps)

See the Grieco Dehydration

O₃, NaHCO₃, Me₂S

CH₂Cl₂, MeOH
-78 °C to RT

n-BuLi

THF
-78 °C, 40 min, 67 % (2 steps)

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

Camphorsulfonic acid

CH₂Cl₂
RT, 8 h

(CF₃CO)₂O, NaOAc, 2,6-Lutidine

Ac₂O
RT, 60 min

See the Pummerer Rearrangement

HgCl₂, CaCO₃

MeCN, H₂O
RT, 2 h, 60 % (2 steps)

Part 2 of 3

MeI, K₂CO₃

Acetone

NaNH₂, CO₂

Et₂O, NH₃

CDI

THF

Me₂SO₄, K₂CO₃

Acetone

Part 3 of 3

i-Pr₂NLi, HMPA

THF
-78 °C, 20 min, 80 %

See the Aldol Addition

TsCl, Et₃N, DMAP

CH₂Cl₂
RT, 12 h, 82 %