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Named reactions

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Search synthesis

Azadirachtin

"The work reported herein represents the conclusion of a 22-year synthesis journey"

Chemical structure of Azadirachtin
C35H44O16

Browse hundreds of other total syntheses.

Part 1 of 3
Chemical structure
n-Bu2SnO
MeOH
Reflux, 2 h
Chemical structure
MeOCH2Cl
Dioxane
55 °C, 90 min, 93 % (2 steps)
Chemical structure
Pyr.SO3, DMSO, i-Pr2NEt
CH2Cl2
0 °C, 30 min

See the Parikh-Doering Oxidation
Chemical structure
AllylMgCl
THF
-78 °C, 30 min, 85 % (2 steps)

See the Grignard Reaction
Chemical structure
BnBr, NaH
DMF
0 °C to RT, 19 h, 92 %

See the Williamson Ether Synthesis
Chemical structure
NBS
MeCN, Buffer (pH = 7)
RT, 90 min, 58 %
Chemical structure
Zn, NH4Cl
EtOH
Reflux, 2 h
Chemical structure
  1. O3
  2. Ph3P
CH2Cl2
-78 °C to RT, 18.5 h
Chemical structure
n-Pr4N+ RuO4-, NMO
4 Å MS
MeCN
RT, 75 min, 76 % (3 steps)

See the Ley-Griffith Oxidation
Chemical structure
CF3CO2H
CH2Cl2, H2O
RT, 97 %
Chemical structure
TBSCl, Et3N, DMAP
DMF
RT, 3 h, 71 %
Chemical structure
  1. TMS2NNa
  2. CS2
  3. MeI
THF
-78 °C, 90 min, 92 %
Chemical structure
n-Bu3SnH, AIBN
PhMe
Reflux, 2 h, 100 %

See the Barton-McCombie Reaction
Chemical structure
CF3CO2H
CH2Cl2, H2O
RT, 81 %
Chemical structure
Pyr.SO3, DMSO, i-Pr2NEt
CH2Cl2
0 °C, 2 h

See the Parikh-Doering Oxidation
Chemical structure
Ph3P+CHBr2 Br-, KOt-Bu
THF
RT, 12 h, 78 % (2 steps)

See the Wittig Reaction
Chemical structure
TMSBr
CH2Cl2
0 °C, 30 min, 100 %
Chemical structure
Cl3C(=NH)OCH2(p-MeOPh), La(OTf)3
THF
RT, 3 h, 90 %
Chemical structure
i-Bu2AlH
CH2Cl2
-78 °C, 2 h, 97 %
Chemical structure
Amberlyst ® 15
3 Å MS
MeCN, MeOH
RT, 16 h, 74 % (2 steps)

Selectivity : 66:34 α/β
Chemical structure
MeLi.LiBr
THF
-78 to -20 °C, 3 h, 97 % (α), 93 % (β)

See the Fritsch-Buttenberg-Wiechell Rearrangement
The epimers are carried out separately.
Chemical structure
  1. i-PrMgBr
  2. (CH2O)n
THF
45 °C, 5.5 h, 89 % (α), 78 % (β)

See the Grignard Reaction
Chemical structure
Ms2O, i-Pr2NEt
CH2Cl2
0 °C, 30 min, 90 % (α), 90 % (β)
Chemical structure

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Part 2 of 3
Chemical structure
+
Chemical structure
n-BuLi, (CH2NMe2)2
THF
-78 to -30 °C, 95 min, 54 %

See the Corey-Seebach Reaction
Chemical structure
+
Chemical structure
KH
THF
0 °C to RT, 90 min, 60 %

See the Williamson Ether Synthesis
Chemical structure
Pyr.HF
MeCN, H2O
RT to 35 °C, 34 h, 85 %
Chemical structure
(COCl)2, DMSO, Et3N
THF
-78 °C to RT, 23 min, 93 %

See the Swern Oxidation
Chemical structure
+
Chemical structure
LiCl, i-Pr2NEt
DMF
RT, 44 h, 34 %

See the Horner-Wadsworth-Emmons Reaction
The yield was 67 % brsm. Also isolated was the Z-isomer (13 % yield).
Chemical structure
Cp2TiMe2, Pyr
PhMe, THF
-50 to -35 °C, 3 h

See the Tebbe-Petasis Olefination
Chemical structure
Hydroquinone, i-Pr2NEt
PhMe
85 °C, 4 h, 21 % (2 steps)

See the Diels-Alder Reaction
The yield was 27 % brsm.
Chemical structure
TsOH
MeCN, H2O
RT to 55 °C, 6.5 h, 45 %
Chemical structure
t-BuCOCl, Pyr, DMAP
CH2Cl2
45 °C, 72 h, 81 %
Chemical structure
NaBH4
THF, MeOH
RT, 90 min, 82 %
Chemical structure
MeI, CaCO3
MeCN, H2O
55 °C, 10 h, 98 %
Chemical structure
DBU
CH2Cl2
RT, 2.5 h, 100 %
Chemical structure
AcOOH, Hg(CF3CO2)2
CF3CH2OH, AcOH
10 °C to RT, 2.5 h, 85 %

See the Fleming-Tamao Oxidation
Chemical structure
PhCHO, Pyr.TsOH
Dean-Stark
PhH
Reflux, 24.5 h, 83 %
Chemical structure
NaBH4, CeCl3.7H2O
MeOH
0 °C, 10 min, 44 %

See the Luche Reduction
Also isolated was the C8-epimer (53 % yield).
Chemical structure
+
Chemical structure
Pyr, DMAP
CH2Cl2
RT to 30 °C, 21 h, 43 %

Also isolated was the corresponding diastereoisomer (44 % yield).
Chemical structure
K2CO3
MeOH
RT, 11 h
Chemical structure
CH2N2
CH2Cl2
RT
Chemical structure
t-BuCOCl, Pyr
CH2Cl2
RT, 45 min, 95 % (2 steps)
Chemical structure
TBSOTf, 2,6-Lutidine
CH2Cl2
0 °C, 40 min, 96 %
Chemical structure
LiOH
EtOH, H2O
60 °C, 5 h
Chemical structure
CH2N2
CH2Cl2
RT, 91 % (2 steps)
Chemical structure
Dess-Martin Periodinane, Pyr
CH2Cl2
13 °C to RT, 25 min, 90 %

See the Dess-Martin Oxidation
Chemical structure
TBSOTf, Et3N
CH2Cl2
-15 to -5 °C, 3 h

The starting material was recovered and recycled.
Chemical structure
  1. O3
  2. Ph3P
CH2Cl2
-78 °C to RT, 13 h, 85 % (2 steps)
Chemical structure
Zn(BH4)2
THF
-10 °C, 6.5 h
Chemical structure
NCCH2CO2H, TsCl, Pyr
CH2Cl2
RT, 20 min, 98 % (2 steps)
Chemical structure
n-Bu4N+ F-
4 Å MS
THF
RT, 4 h, 93 %
Chemical structure
H2Cr2O7.2Pyr
4 ÅMS
CH2Cl2
RT, 3 h, 88 %
Chemical structure
TMS2NLi
THF
0 °C to RT, 100 min, 100 %

Selectivity : 70:30
See the Michael Addition
Chemical structure
DMDO
Acetone
0 °C, 22 min
Chemical structure
Pyr.TsOH
MeOH
RT, 5.5 h, 70 % (2 steps)

Selectivity : 82:18 S/R
Chemical structure
PhCHO, Pyr.TsOH
PhH
Reflux, 4.5 h, 74 %

Selectivity : 75:25 S/R
Chemical structure
BnBr, Ag2O
DMF
RT, 3.5 h, 61 %

Also isolated was the C5-epimer (19 % yield).
Chemical structure
TBSOTf, Et3N
MeCN
RT, 2 h, 77 %
Chemical structure
H2CN+Me2 I-
CH2Cl2
35 °C, 48 h

See the Mannich Reaction
Chemical structure
SiO2
CH2Cl2
RT, 18 h, 68 % (2 steps)

The yield was 97 % brsm.
Chemical structure
H2, Pd/C
1 atm
MeOH
RT, 60 min, 60 %

Selectivity : 80:20 α/β
Chemical structure
The experimental details for this step doesn't seem to be reported anywhere. The product is also obtained by the degradation of natural azadirachtin.
Chemical structure
TESOTf, i-Pr2NEt
CH2Cl2
-60 to 0 °C, 2.5 h, 71 %
Chemical structure

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Part 3 of 3
Chemical structure
+
Chemical structure
NaH, 15-Crown-5
0 °C to RT, 4 h, 82 % (α), 74 % (β)

The epimers are carried out separately.
Chemical structure
n-Bu4N+ F-
THF
0 °C, 10 min, 90 % (α), 100 % (β)
Chemical structure
μW
1,2-Dichlorobenzene
185 °C, 20 min, 86 % (α), 83 % (β)

See the Claisen Rearrangement
Chemical structure
N-TBS-imidazole
DMF
80 °C, 2 h, 91 % (α), 86 % (β)
Chemical structure
DDQ
CH2Cl2, H2O
RT, 3 h, 91 % (α), 95 % (β)
Chemical structure
TMS2NNa, CS2, MeI
THF
-78 °C, 2 h, 86 % (α), 57 % (β)
Chemical structure
n-Bu3SnH, AIBN
PhMe
110 °C, 14 h, 90 % (α), 91 % (β)
Chemical structure
Reagent structure
MMPP, NaHCO3
Sealed tube
MeOH
110 °C, 7 d, 22 % (α), 65 % (β)

See the Prilezhaev Reaction
The yield were 67% (α) and 93 % (β) brsm.
Chemical structure
n-Bu4N+ F-
THF
RT, 60 min, 95 %

The product is also obtained by the degradation of natural azadirachtin.
Chemical structure
H2, Pd/C
1 atm
EtOH
RT, 3 h, 95 %
Chemical structure
Ac2O, Et3N, DMAP
CH2Cl2
RT, 4 h, 76 %
Chemical structure
+
Chemical structure
Cs2CO3
PhMe
6 d, 50 %

See the Yamaguchi Esterification
"Heated in a sealed tube".
Chemical structure
NaBH4, CeCl3.7H2O
MeOH
0 °C, 4 h, 49 %

See the Luche Reduction
Also isolated was the C3-epimer (43 % yield).
Chemical structure
H2, Pd/C
1 atm
MeOH
RT, 14 h, 81 %
Chemical structure
PhSeH, Pyr.TsOH
DCE
Reflux, 4 h
Chemical structure
H2O2, Pyr
CH2Cl2, H2O
0 °C, 10 min, 85 % (2 steps)
Chemical structure

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