The Diels-Alder Reaction

M

MeO2C

CO2Me

MeO2C

C

C CO2Me

CO

Me

+

CO

Me

N

N

2

N

2

N

N

N

Ph

Ph CO2Me

Ph

CO2Me

45

47

48

Reaction conditions

Products (Yield %)

1. DCM, 150 C, 8−10 atm

47 + 48 (18 %)

2. MW, 780 W, 130 C, 6 min

47 (10 %) + 48 (62%)

Ph

CO2Et

Ph

C

C CO2Et

N

N

N

N

Ph

Ph

46

49

Reaction conditions

Product (Yield %)

1. 140 C, 6 d

0

2. MW, 180 W, 180 C, 15 min

19

M

O

O

R1

O 52

R1

O

R2 O

O

R1

! "

Ph

O

R2

N

O

O

50 R1 = R2 = pOMe-C6H4

O

R2

51 R1 = pOMe-C6H4, R2 = Me

N

#

#

#

#

#

#

#

#

#

#

#

#

M

#

#

#

#

1. SiO2/H2O

O

O

O

O

O

MW, 5 min, 64%

+

H

TBSO

! "

O OH 2. TBSCl, 75%

OSBT

H

54

55

56

M

1AN + DP

AD

! "

AN

, DP

O

H

H

O

O

O

+

O

+

O

O

HHO

O

Conditions

endo/exo

Et2O, r.t., very fast

98:2

EtOH, Et3N, hν (300 nm), r.t., 6 h

2:98

O

O

OH

O

H

H

O

H

H

H

Me

H

O

O

H O

H

O

HO

hν, Et3N (5 %)

hν, Et3N (50%)

hν, Et3N (20 %)

hν, Et3N (5%)

Yield : 64%

Yield : 81%

Yield : 70%

Yield : 90%

M

R

R

R

Ph

Ph

hν (250 W), CH3CN

S + Ph C CH

S

r.t., 4.5−24 h, 50−91%

! "

R

R

hν, 28 C

C60 +

! "

9 h

C60

R = H, Me

72