Synthesis of Dysinosin A

Structure of Dysinosin A

C26H44N6O10S

Principal investigator	Stephen Hanessian
Publication year	2002
Synthesis type	Total
Number of steps	32 (3 parts)
References	Tetrahedron Lett. 1998, 39, 5887. J. Am. Chem. Soc. 2002, 124, 13342.

Part 1 of 3

intermediate structure

Na2CO3, Pb(OAc)4

CH2Cl2

0 °C to RT, 2.5 h

See the Criegee Reaction

intermediate structure

NaH2PO4, NaClO2, 2-Methyl-2-butene

t-BuOH

0 °C to RT, ON, 75% (2 steps)

See the Pinnick-Lindgren Oxidation

intermediate structure

+

intermediate structure

HOBt, EDC

CH2Cl2

0 °C to RT, ON, 95%

intermediate structure

H2, Pd/C

1 atm

MeOH

RT, 5 h, 99%

intermediate structure

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Part 2 of 3

intermediate structure

Imidazole, TBDPSCl

DMF

0 °C to RT, ON, 90%

intermediate structure

i-Bu2AlH

CH2Cl2

-78 °C, 20 min, 90%

intermediate structure

AllylNH2, MsCl

CH2Cl2, Et3N

0 °C to RT, ON, 84%

intermediate structure

Boc2O, Et3N

CH2Cl2

RT, 60 min, 100%

intermediate structure

Grubbs catalyst (1st gen.)

CH2Cl2

RT, ON, 90%

See the Olefin Metathesis

intermediate structure

n-Bu4N+ F-

THF

0 °C to RT, 70 min, 92%

intermediate structure

Ph3P, DEAD, (PhO)2P(O)N3

THF

0 °C to RT, 40 min, 82%

See the Mitsunobu Reaction

intermediate structure

CF3CO2H

CH2Cl2

RT, 4 h

intermediate structure

Special reagent

CHCl3

RT, ON, 86% (2 steps)

intermediate structure

AcOH, Ph3P

H2O, THF

60 °C, 60 min, 72%

See the Staudinger Reaction

intermediate structure

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Part 3 of 3

intermediate structure

TMS2NLi
AllylBr

THF

-78 °C, 92%

intermediate structure

CF3CO2H

CH2Cl2

RT, 20 min, 83%

intermediate structure

PhMe

Reflux, 90 min

intermediate structure

TMS2NLi
ClCO2Bn

THF

-78 °C, 2 h

intermediate structure

LiBHEt3

THF

-78 °C, 90 min

intermediate structure

Ac2O, DMAP

CH2Cl2

RT

intermediate structure

BF3.OEt2, AllylSnBu3

PhMe

-78 °C, 5 h, 70% (5 steps)

"Also isolated was the C5-epimer (13 % yield)."

intermediate structure

Grubbs catalyst (1st gen.)

CH2Cl2

RT, 99%

See the Olefin Metathesis

intermediate structure

mCPBA

CH2Cl2

RT, 2 h

See the Prilezhaev Reaction

intermediate structure

CF3CO2H

H2O, THF

RT, ON, 75-79% (2 steps)

intermediate structure

MeOCH2Cl, i-Pr2NEt

CH2Cl2

RT, 18 h, 98%

intermediate structure

H2, Pd(OH)2

1 atm

MeOH

RT, 3 h, 95%

intermediate structure

+

intermediate structure

i-Pr2NEt, BOP-Cl

MeCN

0 °C to RT, 25 h, 83%

intermediate structure

LiOH

MeOH, THF

RT, ON, 97%

intermediate structure

+

intermediate structure

HOBt, EDC

CH2Cl2

RT, 24 h, 95%

intermediate structure

n-Bu4N+ F-

THF

RT, 4 h, 97%

intermediate structure

Pyr.SO3, n-Bu2SnO

CH2Cl2

RT, 6 h

intermediate structure

CF3CO2H

CH2Cl2

RT, 6 h, 35% (2 steps)

intermediate structure

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