Synthesis of Grandisine D

Structure of Grandisine D

C16H21NO2

Principal investigatorOsamu Tamura
Publication year2009
Synthesis typeTotal
Number of steps 17 (linear)
References
Part 1 of 1
intermediate structure
NaBH4, H2SO4
EtOH, H2O
-52 °C to RT, 14 h, 84%
intermediate structure
Acrolein, Grubbs-Hoveyda catalyst (2nd gen.)
CH2Cl2
RT, 2 h, 84%
intermediate structure
TfOH, Me2S
MeCN
-35 °C to RT, 2 h, 67%
intermediate structure + 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
PhOC(S)Cl, DMAP
CH2Cl2
Reflux, 24 h, 100%
intermediate structure
n-Bu3SnH, AIBN
PhH
Reflux, 30 min, 94%
intermediate structure
TsOH
Acetone, H2O
Reflux, 15 min, 97%
intermediate structure + intermediate structure
n-Bu2BOTf, i-Pr2NEt
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%
intermediate structure
PhSH, HClO4
MeOH, H2O
RT, 2 h, 94%
intermediate structure
PhMe, CH2Cl2
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 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