Synthesis of Tunicamycin V

Structure of Tunicamycin V

C38H62N4O16

Principal investigator	Andrew G. Myers
Publication year	1993
Synthesis type	Total
Number of steps	28 (5 parts)
References	J. Am. Chem. Soc. 1993, 115, 2036. J. Am. Chem. Soc. 1994, 116, 4697.

Part 1 of 5

intermediate structure

KF.2H2O

MeOH

RT, 6.5 h, 100%

intermediate structure

K2CO3, Cl3CCN

CH2Cl2

RT, 24 h, 64%

intermediate structure

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Part 2 of 5

intermediate structure

BrCCl3

hv

0 °C, 2.5 h, 87%

See the Hanessian-Hullar Reaction

intermediate structure

i-Pr2NEt, BnOCH2Cl

CH2Cl2

Reflux, 15 h, 89%

intermediate structure

PhSeH, Et3N

0 to 60 °C, 2.5 h, 98%

intermediate structure

Phthaloyl Chloride, Et3N, DBU

CH2Cl2, PhMe

0 to 100 °C, 100 min, 86%

intermediate structure

PhSeH, Et3N

DME

90 °C, 10 h, 95%

intermediate structure

Et3N.3HF

MeCN

RT, 6 h, 97%

intermediate structure

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Part 3 of 5

intermediate structure

+

intermediate structure

TfOH

4A MS

PhMe

-20 °C, 24 h, 77%

intermediate structure

NH2NH2.H2O

EtOH

100 °C, 12 h, 87%

intermediate structure

ClCO2Bn

Pyr

0 °C, 30 min, 91%

intermediate structure

PhSeH

Et3N

55 °C, 12 h, 91%

intermediate structure

Ac2O

Pyr

60 °C, 2.5 h, 91%

intermediate structure

mCPBA

CCl4

-15 to 0 °C, 50 min, 88%

intermediate structure

K2CO3, NaOH

RT, 2 h, 92%

intermediate structure

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Part 4 of 5

intermediate structure

DMAP, Et3N, TMSCl

CH2Cl2

RT, 2 h

"DMT = Dimethoxytrityl"

intermediate structure

DMAP, Boc2O

Pyr

RT, 12 h

intermediate structure

KF.2H2O

MeOH

RT, 3 h, 79% (3 steps)

intermediate structure

ClCO2Allyl

Pyr

-20 to RT, 35 min, 87%

intermediate structure

PhSO3H

CHCl3

RT, 2 min, 76%

intermediate structure

Dess-Martin Periodinane

CH2Cl2

RT, 20 min, 72%

See the Dess-Martin Oxidation

intermediate structure

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Part 5 of 5

intermediate structure

+

intermediate structure

PhSeH
Me2SiCl2

PhMe, Pyr

RT, 6 h, 81%

intermediate structure

Pd(PPh3)2Cl2, n-Bu3SnH

CH2Cl2, H2O

RT, 6 min, 85%

intermediate structure

Et3B, n-Bu3SnH

0 °C, 2 h

intermediate structure

KF.2H2O

MeOH

RT, 2 h, 60% (2 steps)

intermediate structure

Pd, HCO2H

MeOH

RT to 40 °C, 6.5 h

intermediate structure

HF

H2O, MeCN, MeOH

RT, 2 h

intermediate structure

Special reagent

DCC

CH2Cl2, MeOH

RT, 2 d, 83% (3 steps)

intermediate structure

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