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Penitrem D
| Author | Amos B. Smith, III |
|---|---|
| Publication year | 2003 |
| Synthesis type | Total synthesis |
| Number of steps | 56 (3 parts) |
| References |
Browse hundreds of other total syntheses.
Part 1 of 3
Methyl acrylate
hν
CH2Cl2
0 °C, 8.5 h
The product depicted is the major component of an uncharacterized mixture of isomers.
hν
0 °C, 8.5 h
The product depicted is the major component of an uncharacterized mixture of isomers.
HC(OMe)3, Amberlyst ® 15
0 °C, 2.5 h
The product depicted is the major component of an uncharacterized mixture of isomers.
The product depicted is the major component of an uncharacterized mixture of isomers.
MeMgBr
PhH, Et2O
0 °C to RT, 90 min
See the Grignard Reaction
The product depicted is the major component of an uncharacterized mixture of isomers.
0 °C to RT, 90 min
See the Grignard Reaction
The product depicted is the major component of an uncharacterized mixture of isomers.
Pyr.TsOH
Acetone
RT, 2.5 h, 49 % (4 steps)
RT, 2.5 h, 49 % (4 steps)
MeOCH2Cl, i-Pr2NEt
CH2Cl2
0 °C to RT, 74 h
0 °C to RT, 74 h
KOH
MeOH, H2O
Reflux, 71 % (4 steps)
Reflux, 71 % (4 steps)
NH2OH.HCl, NaOAc
MeOH
Reflux, 3 h, 83 %
Reflux, 3 h, 83 %
NaOH
EtOH, H2O
Reflux, ON, 67 % (2 steps)
Reflux, ON, 67 % (2 steps)
H2, Pd(OH)2/C
1 atm
EtOH, MeOH, i-PrOH
RT, 48 h, 96 %
1 atm
RT, 48 h, 96 %
TBSCl, i-Pr2NEt, DMAP
CH2Cl2
0 °C to RT, 3 h, 88 %
The following protection / deprotection sequence was due to a late deviation from the initial plan.
0 °C to RT, 3 h, 88 %
The following protection / deprotection sequence was due to a late deviation from the initial plan.
HCl
MeOH, H2O
RT, 3 h, 89 %
RT, 3 h, 89 %
TIPSCl, DMAP
Et3N
RT, 25 h, 95 %
RT, 25 h, 95 %
TMSCl, DMAP
THF, Et3N
RT, 48 h, 48 %
The yield was 100% brsm.
RT, 48 h, 48 %
The yield was 100% brsm.
Part 2 of 3
O2, Rose Bengal, Ph3P
hν
THF
-78 °C to RT, 24 h, 50 %
hν
-78 °C to RT, 24 h, 50 %
+ 
MeI, KOt-Bu, Ph2SO
THF
0 °C to RT, 4 h, 59 %
0 °C to RT, 4 h, 59 %
Pyr.TsOH
Acetone, H2O
RT, 24 h, 98 %
RT, 24 h, 98 %
Zn, NiCl2.6H2O
Ultrasound
2-Methoxyethanol, Buffer (pH = 9)
RT, 27 h, 90 %
Ultrasound
RT, 27 h, 90 %
O3, Me2S
CH2Cl2, MeOH
-78 °C to RT, ON, 86 %
R = Bn, Bz (mixture)
-78 °C to RT, ON, 86 %
R = Bn, Bz (mixture)
KMnO4, NaH2PO4
t-BuOH, H2O
RT, 90 min
R = Bn, Bz (mixture)
RT, 90 min
R = Bn, Bz (mixture)
CH2N2
Et2O, CH2Cl2
RT, 92 % (2 steps)
Selectivity : 89:11
R = Bn, Bz (mixture)
RT, 92 % (2 steps)
Selectivity : 89:11
R = Bn, Bz (mixture)
H2, Pd(OH)2
1 atm
EtOH, H2O
RT, 24 h, 92 %
R = Bn, Bz (mixture); R = H, Bz (mixture)
1 atm
RT, 24 h, 92 %
R = Bn, Bz (mixture); R = H, Bz (mixture)
KOt-Bu
MeOH
Reflux, 3 h, 86 %
R = H, Bz (mixture)
Reflux, 3 h, 86 %
R = H, Bz (mixture)
Neopentyl glycol, Camphorsulfonic acid
Dean-Stark
PhH
Reflux, 6 h, 96 %
Dean-Stark
Reflux, 6 h, 96 %
i-Bu2AlH
CH2Cl2
-78 °C, 20 min, 83 %
-78 °C, 20 min, 83 %
HCl
MeOH
0 °C to RT, 2 h, 96 %
Selectivity : 55:45 S/R
Both C1-epimers were separated and the following steps were carried in separate vessels.
0 °C to RT, 2 h, 96 %
Selectivity : 55:45 S/R
Both C1-epimers were separated and the following steps were carried in separate vessels.
Me2NNH2, AcOH, MgSO4
PhH
RT, 2 h, 94 % / 91 %
Mixture of E and Z hydrazones.
RT, 2 h, 94 % / 91 %
Mixture of E and Z hydrazones.
+ 
i-Pr2NLi
-78 to 65 °C, 5.5 h
BzCl, DMAP
CH2Cl2
RT, 18 h, 76 % / 60 % (2 steps)
RT, 18 h, 76 % / 60 % (2 steps)
AcOH, NaOAc
PhH
65 °C, 14 h, 53 % / 56 %
65 °C, 14 h, 53 % / 56 %
HClO4
MeCN, H2O
55 °C, 2 h, 90 % / 74 %
55 °C, 2 h, 90 % / 74 %
H2Cr2O7.2Pyr
CH2Cl2
RT, 5 h, 78 %
RT, 5 h, 78 %
TfOH, Et3SiH
PhMe
-40 °C to RT, 90 min, 60 %
-40 °C to RT, 90 min, 60 %
K2CO3
MeOH, H2O
55 °C, 15 h
55 °C, 15 h
EDC, DMAP
CH2Cl2
RT, 60 min, 90 % (2 steps)
RT, 60 min, 90 % (2 steps)
O2, SiO2
1 atm
EtOAc
RT, 40 h, 72 %
1 atm
RT, 40 h, 72 %
Ph3P
PhH
RT, 60 min, 93 %
RT, 60 min, 93 %
Li(s-Bu)3BH
THF
-78 °C, 20 min
-78 °C, 20 min
TESOTf, 2,6-Lutidine
CH2Cl2
RT, 60 min, 72 % (2 steps)
RT, 60 min, 72 % (2 steps)
Part 3 of 3
+ 
HCl
THF, H2O
RT, 60 min, 89 %
RT, 60 min, 89 %
Sc(OTf)3
PhH
RT, 60 min, 62 %
RT, 60 min, 62 %
Ac2O, DMAP
CH2Cl2, Et3N
RT, 60 min, 80 %
RT, 60 min, 80 %
n-Bu4N+ F-
THF
RT, 30 min, 84 %
RT, 30 min, 84 %
o-NO2PhSeCN, n-Bu3P
THF
RT, 15 min, 81 %
RT, 15 min, 81 %
K2CO3
MeOH
RT, 4 h, 82 %
RT, 4 h, 82 %
