Synthesis of Thielocin A1b

Structure of Thielocin A1b

C54H60O18

Principal investigator	Robert N. Young
Publication year	2001
Synthesis type	Total
Number of steps	21 (4 parts)
References	J. Am. Chem. Soc. 1994, 116, 759. J. Am. Chem. Soc. 2001, 123, 11381.

Part 1 of 4

intermediate structure

HMTA

CF3CO2H

Reflux, 12 h, 39%

See the Duff Reaction

intermediate structure

H2SO4, Cl3CCH2OH

RT, 5 d, 61%

intermediate structure

K2CO3, Me2SO4

Acetone

50 °C, 3 h, 90%

intermediate structure

Et3SiH

CF3CO2H

RT, 15 h, 96%

intermediate structure

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Part 2 of 4

intermediate structure

NaBH3CN, Piperidine

AcOH, MeCN

RT, 83%

intermediate structure

NaH, TBSCl

Et3N

RT, 95%

intermediate structure

MeOTf

CH2Cl2

0 °C to RT, 30 min, 99%

intermediate structure

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Part 3 of 4

intermediate structure

HCl, HgCl2, Zn

EtOH, H2O

Reflux, 2 h, 88%

See the Clemmensen Reduction

intermediate structure

TMS(CH2)2OH, NaH

PhH

120 °C, 4 h, 63%

intermediate structure

TBDPSCl, Et3N, DMAP

CH2Cl2

RT, 96 h, 91%

intermediate structure

PhI(OAc)2

AcOH

RT, 5 h, 57%

intermediate structure

LiOH, 12-Crown-4

H2O, THF

RT, 15 h, 70%

intermediate structure

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Part 4 of 4

intermediate structure

+

intermediate structure

n-Bu4N+ F-

DMF, THF

-20 °C to RT, 3.5 h, 95%

intermediate structure

CDI

Et3N

RT, 1 h, 98%

intermediate structure

n-Bu4N+ F-

DMF, THF

RT, 15 h, 67%

intermediate structure

MeOCHCl2

CH2Cl2

Reflux, 3 h

intermediate structure

Special reagent

Et3N

CH2Cl2

RT, 15 h, 83 % (2 steps)

intermediate structure

Cd

AcOH, DMF

RT, 15 h, 84 %

intermediate structure

Special reagent

(CF3CO)2O

PhH

RT, 15 h, 83%

intermediate structure

Cd

AcOH, DMF

RT, 15 h, 80%

intermediate structure

NaOH

Dioxane , H2O

-10 °C, 8-10 h, 59%

intermediate structure

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