Synthesis of Aspidophytine

Structure of Aspidophytine

C22H26N2O4

Principal investigator	Elias J. Corey
Publication year	1999
Synthesis type	Total
Number of steps	20 (3 parts)
References	J. Am. Chem. Soc. 1999, 121, 6771.

Part 1 of 3

intermediate structure

SiO2, Fe

AcOH, PhMe

Reflux, 20 min, 71%

See the Leimgruber-Batcho Indole Synthesis

intermediate structure

KOH, MeI, n-Bu4N+ I-

THF

RT, 3 h, 94%

intermediate structure

POCl3

DMF

0 to 35 °C, 60 min, 99%

See the Vilsmeier-Haack Formylation

intermediate structure

NH4OAc

MeNO2

Reflux, 60 min, 92%

See the Henry Reaction

intermediate structure

LiAlH4

THF

0 °C to Reflux, 60 min, 88%

intermediate structure

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Part 2 of 3

intermediate structure

+

intermediate structure

CeCl3

THF

0 °C, 82%

See the Grignard Reaction

intermediate structure

Catecholborane, CBS Reagent

CH2Cl2

-78 °C, 10 h, 94%

See the Itsuno-Corey Reduction

intermediate structure

Na(Hg)

MeOH

RT, 2 h, 82%

intermediate structure

DMAP, Ac2O

CH2Cl2, Et3N

RT, 60 min, 97%

intermediate structure

i-Pr2NLi
TBSCl

THF

-78 °C to Reflux, 4.5 h

See the Ireland-Claisen Rearrangement

intermediate structure

EDC, DMAP

i-PrOH

40 °C, 3 h, 57% (2 steps)

intermediate structure

OsO4, NMO

Acetone, H2O

RT, 6 h, 57%

See the Upjohn Dihydroxylation

intermediate structure

NaIO4

H2O, THF

RT, 35 min, 98%

intermediate structure

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Part 3 of 3

intermediate structure

+

intermediate structure

NaBH3CN, (CF3CO)2O

MeCN

0 °C to RT, 2.5 h, 66%

See the Hosomi-Sakurai Reaction

intermediate structure

NaOH

EtOH

75 °C, 20 h, 88%

intermediate structure

K3Fe(CN)6, NaHCO3

H2O, t-BuOH

RT, 5 min, 92%

intermediate structure

OsO4, DMAP

H2O, t-BuOH

intermediate structure

Pb(OAc)4

AcOH, CH2Cl2

-20 °C, 10 min, 71% (2 steps)

See the Criegee Reaction

intermediate structure

TMS2NK
PhNTf2

THF

-78 °C, 30 min, 54%

intermediate structure

n-Bu3SnH, Pd(PPh3)4

THF

RT, 60 min, 86%

See the Stille Coupling

intermediate structure

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