Synthesis of Grandisine D

Structure of Grandisine D

C16H21NO2

Principal investigator	Osamu Tamura
Publication year	2009
Synthesis type	Total
Number of steps	17 (linear)
References	Org. Lett. 2009, 11, 1179.

Part 1 of 1

intermediate structure

AcCl

Reflux

intermediate structure

+

intermediate structure

Et3N

CH2Cl2

0 °C to RT, 5 h

intermediate structure

AcCl

Reflux, 90 min, 90% (3 steps)

intermediate structure

H2SO4, NaBH4

EtOH, H2O

-52 °C to RT, 14 h, 84%

intermediate structure

Acrolein, Grubbs-Hoveyda catalyst (2nd gen.)

CH2Cl2

RT, 2 h, 84%

See the Olefin Metathesis

intermediate structure

Me2S, TfOH

MeCN

-35 °C to RT, 2 h, 67%

See the Morita-Baylis-Hillman Reaction

intermediate structure

(CH2OH)2, TsOH

PhH

Reflux, 13 h, 88%

"Also isolated was the C8a-epimer (8 % yield)."

intermediate structure

NaOEt

EtOH

4 °C to RT, 10 h, 70%

intermediate structure

DMAP, PhOC(S)Cl

CH2Cl2

Reflux, 24 h, 100%

intermediate structure

n-Bu3SnH, AIBN

PhH

Reflux, 30 min, 94%

See the Barton-McCombie Reaction

intermediate structure

TsOH

Acetone, H2O

Reflux, 15 min, 97%

intermediate structure

+

intermediate structure

i-Pr2NEt, n-Bu2BOTf

CH2Cl2

-78 °C to RT, 2 h, 100%

See the Aldol Addition

intermediate structure

Dess-Martin Periodinane

CH2Cl2

4 °C to RT, 3 h, 88%

See the Dess-Martin Oxidation

intermediate structure

HClO4, PhSH

H2O, MeOH

RT, 2 h, 94%

intermediate structure

Special reagent

CH2Cl2, PhMe

65 °C, 15 min, 81%

intermediate structure

Me3O+BF4-

MeCN

4 °C to RT, 60 min

intermediate structure

NaBH3CN

MeOH

RT, 60 min, 63% (2 steps)

intermediate structure

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