Synthesis of Stigmatellin A

Structure of Stigmatellin A

C30H42O7

Principal investigator	Dieter Enders
Publication year	2000
Synthesis type	Total
Number of steps	22 (4 parts)
References	Chem. Eur. J. 2000, 6, 1302.

Part 1 of 4

intermediate structure

H3PO4, P2O5

EtCO2H

70 °C, 60 min, 73%

See the Friedel-Crafts Acylation

intermediate structure

mCPBA, CF3CO2H

CH2Cl2

5 °C, 16 h, 87%

See the Baeyer-Villiger Oxidation

intermediate structure

HCl

H2O, MeOH

Reflux, 2 h, 99%

intermediate structure

i-Pr2NEt, MeOCH2Cl

CH2Cl2

0 °C to RT, ON, 98%

intermediate structure

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Part 2 of 4

intermediate structure

DEAD, 4-Methoxyphenol, Ph3P

CH2Cl2

0 °C to RT, 3 d, 95%

See the Mitsunobu Reaction

intermediate structure

NaI

Acetone

Reflux, 5 d, 83%

See the Finkelstein Reaction

intermediate structure

+

intermediate structure

i-Pr2NLi

Et2O

-100 °C to RT, ON, 80%

intermediate structure

MMPP

MeOH, Buffer (pH = 7)

-15 °C, 15 min, 87%

intermediate structure

+

intermediate structure

TiCl4, i-Pr2NEt

CH2Cl2

-78 °C to RT, 3.5 h, 64%

See the Aldol Addition

intermediate structure

Me4N+ BH(OAc)3-, AcOH

MeCN

-40 to -20 °C, 3 d, 99%

See the Evans-Saksena Reduction

intermediate structure

KH , 18-Crown-6
MeI

THF

0 °C to RT, 2 d, 77%

See the Williamson Ether Synthesis

intermediate structure

(NH4)2Ce(NO3)6

H2O, MeCN

0 °C, 6 min, 90%

intermediate structure

H2Cr2O7.2Pyr

DMF

RT, ON, 100%

intermediate structure

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Part 3 of 4

intermediate structure

+

intermediate structure

NaH

THF

-78 °C to RT, ON, 71%

See the Horner-Wadsworth-Emmons Reaction

intermediate structure

i-Bu2AlH

Et2O

-78 °C, 60 min, 99%

intermediate structure

PBr3

Et2O

0 °C, ON, 93%

intermediate structure

P(OEt)3

160 °C, ON, 63%

See the Michaelis-Arbuzov Reaction

intermediate structure

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Part 4 of 4

intermediate structure

+

intermediate structure

DMAP, t-BuCOCl, i-Pr2NEt

CH2Cl2

RT, 3.5 h, 57%

intermediate structure

NaOMe

MeOH

Reflux, 2 h, 75%

See the Baker-Venkataraman Rearrangement

intermediate structure

Pd/C, H2

1 atm

MeOH

RT, 6 min, 74%

intermediate structure

i-Pr2NEt, DMSO, (COCl)2

CH2Cl2

-78 °C to RT, 40 min

See the Swern Oxidation

intermediate structure

+

intermediate structure

i-Pr2NLi

THF

-78 °C to RT, ON, 77% (2 steps)

See the Horner-Wadsworth-Emmons Reaction

intermediate structure

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