Diels-Alder Reaction

Schematic representation of the Diels-Alder Reaction.
Mechanism of the Diels-Alder Reaction
Mechanism of the Diels-Alder Reaction
Sample reactions
intermediate structure
2-Chloroacrylonitrile, Cu(BF4)2
0 °C
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intermediate structure
Et2NH
Et2O
-20 °C, , 40% (3 steps)
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intermediate structure intermediate structure
THF
-78 °C to RT, , 23%
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intermediate structure intermediate structure
PhH
Reflux, 60 min, 100%
"Mixture of isomers."
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intermediate structure intermediate structure
PhH
Reflux, 10 h, 8%
""[This method was not] investigated extensively with a view to determining optimum conditions.""
intermediate structure
intermediate structure
Methyl acrylate, AlCl3
CH2Cl2
-78 °C, 7 h, 98%
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intermediate structure
DBAD
intermediate structure
intermediate structure intermediate structure
CH2Cl2
RT, 36 h
intermediate structure intermediate structure
intermediate structure
1,3-Butadiene
PhH
100 °C, 96 h, 86%
intermediate structure
intermediate structure
PdCl2, NaOAc
MeOH, H2O
38 °C to RT, 3 h, 46%
intermediate structure
intermediate structure
2-Chloroacrylonitrile
PhH
130 °C, 72 h, 85%
intermediate structure
intermediate structure intermediate structure
PhB(OH)2, Neopentyl glycol
PhH
RT to Reflux, 48.5 h, 61%
intermediate structure
intermediate structure
O2, Tetraphenylporphyrin
CH2Cl2
RT, 7 h
intermediate structure
intermediate structure intermediate structure
CH2Cl2
RT, 20 h, 47% (2 steps)
"95 % yield based on the alkene."
intermediate structure
intermediate structure intermediate structure
PhH
90 °C, 5 h, 55%
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intermediate structure intermediate structure
BF3.OEt2
PhMe
-78 °C, 85 min, 59%
"The product was separated from the resulting three diastereoisomers."
intermediate structure
intermediate structure intermediate structure
SnCl4
PhH
RT, , 73%
"The enantiomers were resolved with (+)- and (-)-phenylethylamine."
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intermediate structure intermediate structure
PhH
RT, 2-3 weeks, 93%
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intermediate structure intermediate structure
PhMe
90 °C, 24 h, 88%
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intermediate structure intermediate structure
CCl4
Reflux, 2 h, 100%
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intermediate structure intermediate structure
PhMe
Reflux, 60 min, 92%
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intermediate structure
Maleic anhydride
PhH
80 °C, 12 h, 98%
intermediate structure
intermediate structure intermediate structure
SnCl4
MeCN
RT, 24 h
intermediate structure
intermediate structure intermediate structure
i-Pr2NLi
THF
-78 to 0 °C, 3 h, 88%
intermediate structure
intermediate structure
PhMe
2.5 h, 97%
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intermediate structure
I2, DEAD
THF
4.4%
intermediate structure
intermediate structure
Pyrrolidine
MeOH
60 °C, 4.5 h, 78%
intermediate structure
intermediate structure intermediate structure
98-105 °C, 120 h, 61%
intermediate structure
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PhMe
300 °C, 8 h, 23%
"The yield was 76 % brsm."
intermediate structure intermediate structure
intermediate structure
PhMe
250 °C, 22 h, 44%
"Also isolate was the C14-epimer (24 % yield)."
intermediate structure
intermediate structure
1,3-Butadiene
Dioxane
85-87 °C, 72 h, 66%
intermediate structure
intermediate structure
1,3-Butadiene
PhMe
"No yield given."
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BHT
PhMe
120 °C, 24 h, 92%
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RT, 30 h, 97%
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intermediate structure
Acrolein
MeCN, H2O
RT, 14 h
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intermediate structure
Et3N
Decalin
235-240 °C, 24 h, 55%
"The yield was 70 % brsm. Also isolated was the C2-epimer (14 % yield)."
intermediate structure
intermediate structure
MgI2
PhMe
150 °C, 3 h, 95%
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PhH
185-200 °C, 4 h, 99%
intermediate structure
intermediate structure
PhNEt2
Reflux, 60 min, 100%
intermediate structure
intermediate structure
KOt-Bu
THF
80 °C, 3.5 h, 64%
intermediate structure
intermediate structure
NH3
CH2Cl2
0 °C to RT, 60 min, 47% (2 steps)
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H2O
DMSO
155 °C, 3.5 h, 86%
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80-85 °C, 24 h, 36%
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Mesitylene
160 °C, 72 h, 85%
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n-Pr4N+ IO4-
CHCl3
0 °C, , 57%
"Also isolated was the C-4a epimer (31 %)"
intermediate structure
intermediate structure intermediate structure
ZnCl2
THF
-80 °C to RT, 16 h, 51%
intermediate structure
intermediate structure
NaOH
MeOH
Reflux, 2 h, 60% (2 steps)
intermediate structure
intermediate structure intermediate structure
PhH
Reflux, 2 h, 90%
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Et2O
0 °C, 60 min, 100%
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intermediate structure
Hydroquinone, i-Pr2NEt
PhMe
85 °C, 4 h, 21% (2 steps)
"The yield was 27 % brsm."
intermediate structure
intermediate structure intermediate structure
Me2AlCl
CH2Cl2
-78 °C, 15 min, 79%
intermediate structure
intermediate structure intermediate structure
PhMe
120 °C, 24 h, 91%
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Mesitylene
Reflux, 24 h, 70%
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intermediate structure intermediate structure
Ac2O
125 °C, 30 h, 74%
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intermediate structure intermediate structure
PhH
RT, 3 h
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intermediate structure intermediate structure
110 °C, 3 d, 87%
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