Synthesis of Malayamycin A

Structure of Malayamycin A

C13H18N4O7

Principal investigatorStephen Hanessian
Publication year2003
Synthesis typeTotal
Number of steps 24 (linear)
References
Part 1 of 1
intermediate structure
2,2-Dimethoxypropane, Pyr.TsOH, Na2SO4
94%
intermediate structure + intermediate structure
t-BuLi
75%
intermediate structure
Li(s-Bu)3BH, ZnCl2
CH2Cl2
86%
intermediate structure
DIAD, Ph3P
THF
91%
intermediate structure
AcOH
H2O
85%
intermediate structure + intermediate structure
Pyr
89%
intermediate structure
  1. NaH
  2. (4-MeOPh)CH2Br
DMF, THF
84%
intermediate structure
HCl
Dioxane , H2O
88%
intermediate structure
DMSO, (COCl)2, i-Pr2NEt
CH2Cl2
See the Swern Oxidation
intermediate structure
Ph3P+CH3 Br-, TMS2NNa
THF
36% (2 steps)
See the Wittig Reaction
intermediate structure
  1. NaH
  2. AllylBr
DMF
0 °C to RT, 2 h, 93%
intermediate structure
Grubbs catalyst (1st gen.)
CH2Cl2
Reflux, 5.5 h, 89%
intermediate structure
NBS
THF, H2O
RT, 2 h
intermediate structure
NaOH
THF
Reflux, 45 min
intermediate structure
NaN3
2-Methoxyethanol
126 °C, 75 min, 41% (3 steps)
intermediate structure
Dess-Martin Periodinane
CH2Cl2
RT, 3.5 h
intermediate structure
NaBH4
MeOH
0 °C, 10 min
intermediate structure
  1. NaH
  2. MeI
DMF
0 °C to RT, 2 h, 93% (3 steps)
intermediate structure
DDQ
CH2Cl2, H2O
RT, 60 min, 84%
intermediate structure
t-BuCOCl, DMAP
Pyr, Et3N
RT, 36 h
intermediate structure
TMSCl, NaI
MeCN
RT, 16 h, 42% (2 steps)
intermediate structure
Me3P
THF, H2O
RT to Reflux, 35 min
intermediate structure
Cl3CC(O)NCO
CH2Cl2
RT, 30 min
intermediate structure
MeNH2
MeOH, H2O
RT, 52 h, 60% (3 steps)
intermediate structure