The Diels-Alder Reaction

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HSVM			n
r.t., 1 h
+	C60	n = 1	19%
C60	+	n = 2	15%
		C60

C60

11%

M

+	DCM, −78 C
O	ClO4 , 15 V	endo/exo = 4.7
O	3.5 h, 70%
		O O

M

		H
1. I2, DMF, 25 C, 9 h
N	I , 85%	N
2. n-BuN		H
O
		O

9 examples

M

^ ` ^

M

M

M

M

M

M

(CH2)n	R3	12−15 kbar		(CH2)n	R3			(CH2)n		R3
	+
					R2					R2
		EtAlCl2, 35-65%
	R2			O H					O H R1		! "
O	R1	n = 1, 2			R1
1	3			4			6
2	R1, R2, R3= H, Me			5			7

M M

M

M

$

$

O		CO2R			O CO2R
		R1			H
				r.t.	R1
	+		15 kbar,
			DCM, 60−92%		R2
		R2
		R3			H	! "
O					O R3
8		9			10

R, R1, R2, R3 = H, Me, Et, CH2OSMDBT

M

M
		R1				H	R1
			10−12 kbar, 40−50 C
O					O
			48−65 h, 85−90 %
+	R2				O	R2	! "
O
						H
11	12		a R1 = H, R2 = OSMT			13
			b R1 = OSMT, R2 = OMe

M

M

O	CO	Me	O	CO2Me
H	2		H	H
	+		17 kbar, DCM
			65 C, 48 h, 75%
H			H	H
O O O	OMe		O O	O OMe
14	15			16

O CO2Me

OH

OH O

OH

17

M

M

	X			X
	Y	15 kbar, r.t.		Y
	+
R		4-12 h		R
19	18 a, X = OAc			20
	b, X = OMe

M
R1		OEt
	CO2CH2R
	21	22
	R, R1= H, Me, CO2Me

M

M

					Adducts (%)
			O O	AlCl3	TiCl4	TiCl2-TADDOL
		O		61	46	31
			H
			SePh
			25
	O O		O O
O	+	16 kbar		6	28	35
		O
		82-87%	H
	SePh
			SePh
	23	24	26
			O O
		O		33	26	34

H

SePh

27