Synthesis of 6-Demethyl-6-deoxytetracycline

C21H22N2O7
Principal investigator | Robert B. Woodward |
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Publication year | 1962 |
Synthesis type | Total |
Number of steps | 24 (linear) |
References |
Part 1 of 1
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H2SO4
AcOH, H2O
Reflux, 24 h



H2,
Pd/C
14 atm
AcOH
30 °C, 2 h

H2SO4
CHCl3, MeOH
Reflux, 24 h, 69% (2 steps)
See the Fischer-Speier Esterification
"This step was required for purification purposes (3.3 kg scale!)"

NaOH
H2O
100 °C, 18 h

I2,
Cl2
AcOH
12-17 °C, 7.5 h

HF
H2O
15 °C, 18 h, 63% (3 steps)



HCl
AcOH, H2O
90-94 °C, 45 min, 73%




NaBH4
DME, H2O
-78 to °C, 30 min, 53% (2 steps)


Zn
HCO2H
RT, 1 min, 81%

H2,
Pd/C
3 atm
Et3N, EtOH
RT, 3 h, 91%

Et3N,
ClCO2i-Pr
CHCl3
0 °C, 30 min


MeCN
RT, ON


HBr
H2O
100 °C, 20 min, 9-15% (4 steps)
"Yield BRSM"

O2,
CeCl3.7H2O
DMF, MeOH, Buffer (pH = 10.4)
RT, 15 min

CaCl2,
HCl
H2O, n-BuOH, Ethanolamine
Reflux, 3.5 h, 6% (2 steps)
