Synthesis of Kinamycin F

Structure of Kinamycin F

C18H14N2O7

Principal investigatorKyriacos C. Nicolaou
Publication year2007
Synthesis typeTotal
Number of steps 27 (3 parts)
References
Part 1 of 3
intermediate structure + intermediate structure
AgNO3, (NH4)2S2O8
MeCN, H2O
65 °C, 3.5 h, 75%
intermediate structure
BnBr, Ag2O
CH2Cl2
RT, 18 h, 92%
intermediate structure
Na2S2O4
Et2O, EtOAc, H2O
RT, 30 min
intermediate structure
NaH, MeI
DMF
-15 °C, 60 min, 82% (2 steps)
intermediate structure
KOt-Bu
THF
0 °C, 2 h, 98%
intermediate structure
OsO4, NaIO4
THF, H2O
70 °C, 18 h, 84%
intermediate structure
Part 2 of 3
intermediate structure
  1. MeMgBr
  2. CuBr.Me2S
  3. TMSCl
THF, HMPA
-78 °C to RT, 2.5 h
"The starting material was 90:10 er."
intermediate structure
Pd(OAc)2, O2
DMSO
RT, 18 h, 90% (2 steps)
intermediate structure
OsO4, NMO
Acetone, H2O
RT, 45 min, 76%
"Cristallized thrice to >99:01 er."
intermediate structure
2-Methoxypropene, Camphorsulfonic acid
THF
RT, 18 h, 95%
intermediate structure
  1. TMS2NLi
  2. TMSCl
THF
0 °C, 30 min
intermediate structure
Pd(OAc)2, O2
DMSO
RT, 18 h, 84% (2 steps)
intermediate structure
I2
Pyr, CH2Cl2
RT, 30 min, 92%
intermediate structure
Part 3 of 3
intermediate structure + intermediate structure
Cu, CuI, Pd2(dba)3
DMSO
65 °C, 2.5 h, 83%
intermediate structure
Et3N
CH2Cl2
45 °C, 4 h, 78%
intermediate structure
Ac2O, Et3N, DMAP
CH2Cl2
RT, 20 h, 95%
intermediate structure
SmI2, MeOH
THF
-78 °C, 10 min
intermediate structure
Et3N
CH2Cl2
RT, 60 min, 81% (2 steps)
intermediate structure
SeO2
Dioxane
110 °C, 9 h, 72%
intermediate structure
HF
MeCN, H2O
RT, 3 h
intermediate structure
Ac2O, Et3N, DMAP
CH2Cl2
RT, 20 min, 89% (2 steps)
intermediate structure
H2, Pd/C
EtOAc, AcOH
RT, 3 h, 99%
intermediate structure
TBSCl, Imidazole
DMF
RT, 3 h, 94%
intermediate structure
TsNHNH2, HCl
i-PrOH, H2O
RT, 18 h, 95%
intermediate structure
(NH4)2Ce(NO3)6
MeCN, Buffer (pH = 7)
0 °C, 60 min, 42%
intermediate structure
HCl
MeCN, H2O
RT, 3 h, 95%
intermediate structure
LiOH
THF, H2O
RT, 60 min, 92%
intermediate structure