The Diels-Alder Reaction

CH2=CHSnBu3 Pd(PPh3)4, PhMe 110 C, 4 h, 65%

95

97 Br

PhMe

∆, 2 h, 84%

(+)− 94

Br

O

Tol

SO

O

S-(+)94

O

(+) 94

O

O

4 kbar, 4 d, 12%

O

93 (M)

O
	1. Me2SO4/K2CO3
	Et2O, Na2S2O4
O	2. CH2=CHSnBu3
	Pd(PPh3)4, PhMe	96
	110 C, 4 h, 63%
		12 kbar
		DCM
		48 h
		12%
	O	CAN
		MeCN
		r.t., 2 h
	O	59%
	O
	O
	93 (P)

OMe

OMe

(+) 94

M
	H
	H O	10% Pd-C	O
EtAlCl2,
	99		100
0 C, 6 h, 75%
O
OAc	H
98			O
	O
	H	10% Pd-C
EtAlCl2, 10 kbar	101		102
35 C, 14 h, 42%

M

O		H			H O
				+
98 OAc	A or B	H		H	H
		H	O
		107		108
		A: EtAlCl2, 0 C, 75%, 107/108 = 1
		B: 10 kbar, 35 C, 68%, 107/108 = 6
103			H

10 kbar, 35 C

14 h, 60%

HH O

106 O

O		H
		O
	10 kbar, 35 C	H
		H
98 OAc	66 h, 70%

	O
104	H		H
7 kbar, 50 C	H		O
		+	H
3 h, 70%	H

106 O

		A or B		10% Pd-C
	O			56%
		O		O
	98 OAc	A: DCM, 0 C, 2.5 h, 75% one stereoisomer
		B: 9 kbar, DCM, 30		C, 17 h, 74% two stereoisomers

105

O

	106 O 1. 7 kbar, DCM
	35 C, 6 h, 43%	+
	2. 10% Pd-C	O
	53%
	109	110
		109/110 = 3.5

M

M

	OSMT	C, 75%				OSMT H+
	140						O
F3C Ph	+			C		80%
	or 15 kbar, 80% F						! "
	OMe		3	Ph		F3C
					OMe	Ph
111	12b						112
CF3	OSMT				OMe		F3C
					CF3
						H+
	15 kbar, 50 C
	+	66 h					! "
	OMe		TMSO		H	O
							H

11312b

H

H O

116b

1.12 kbar, ZnCl2, 58%

2.KOH

		O	51
	H			115a	H
	115b				H
	H			1. 12 kbar, ZnCl2,
	1. 12 kbar, ZnCl2, 72%
	2. KOH	98	OAc	19 h, 95%
				2. KOH	O
	O
	116a	O

114

M

M

M

O

117

O

O

O

H O

O

H

O

H

N

Ph

H

N

O

Ph

O

H

O

1:1

+

O

+

1.5:1

CSA, 20 kbar,

20 kbar, DCM,

O

DCM, 4 d, 52%

14 d, 27%

118

O

O

O

H O

H

O

H

H N

Ph

DIEA,

O

20 kbar, DCM,

O

O

7 d, 53%

O

O

H O

+

HO O

H

H O

O

O

1:1.7

O

OH

n

O

O

O

C60

O

C60

3 kbar, 130 C

O

n

n

24 h, 82−85%

n = 1 119

n = 2

120

H+

O

OH

C60

n

n

n

3 kbar, 130 C

O

C60

71−81%

121

n = 1, 2

123

122

124

M

M

O

O O O

H

H O ∆V (IPB)= −21.4 cm3 mol−1

∆V (DMF)= −16.8 cm3 mol−1

O O

O

125		O
							(IPB)= −30.0 cm3 mol−1
		H	∆V
		H	∆V				(DMF)= −27.8 cm3 mol−1

M

O

R

R=H 125

R=OMe 126

O

OMe

+

128

O

OMe

+

129

		O		R
		R H		O
		H
O			+
		O		H	O
10 kbar, PhMe
				H
+
100 C, 10 h, 20%	R
28		O		O
					O
		H
			+
		H O
				127
		O		MeO
O				O
		OMe
10 kbar, PhMe		H	+	H
150 C, 30 h, 61%		H O			! "
				H
				O
28
	O		O	MeO
O				O
			OMe
	OMe
10 kbar, PhMe
			H
	H				! "
150 C, 30 h, 67%	H O	+	H	+
28		O		HH O

O				O
			Ph	R H
	R
		O	N O 10 kbar	H
	+
				O +
				O N
				Ph
R= H	125			131
R= OH	130

O

R O

N Ph

H ! "

H O

132

M

O						R
					O	O MeO2C
R	O	1.	3 kbar, PhCl,				CO2Me
	+	CO2Me	100−130	C, 12 h	R	+	! "
			120−130	C	+
		2.
	133	CO2Me					O

R = H, OMe, OH, Cl

M

M

$ $

$ $ $

	O		O	O	O
		+	+		CN
					+
			CN	CN
	CN
			CH2=CH2CN	6−10 kbar
O				DCM or PhMe
O	R	R2	R1
R1			O		O
		O	R
R2				C60
135		134
O		3 kbar		3 kbar, PhMe	C60
		11−36%

125

H

R2O R, R1, R2 = H, OMe

R

R1

136

M

M

	O
Br	N-Ph
O	O
O
	70%
HO
O	N-Ph

	O
O	N-Ph
O	O
Br	44%
H O

ON-Ph

O

O

Br

R-CH=CH2; (R=Ph, CN)

48-77%

O O

137

O

O

O R-CH=CH2; (R=Ph, CN)

44-63%

Br

O

138

Br

O

R

+

Br

O R

H

O

Br

R

+

O

BrR

H

M

M