The Diels-Alder Reaction

M

CO2Me

	O
		OSMT	SPh	MeO2C
				SMe
OMe
15	28	29	30	31

M

M

E	O	OMe	1. DCM, 13 kbar,	E O	E O	MeO	E	O
			35 C, 7 d, 85%
		+		+		+
			2. CSA
				O
			O			O
			OSMT
			E= CO2Me
32		12b		34	35	36

O

O

33

M

M

O	OAc			O	OAc
				H
	+		6 kbar; 80 C
			3 d; 78%		! "
				H
	OSBT				OSBT
37	38				39

O	H	O	H
		H		OSMT
	OSMT	15 kbar; 50 C
	+	60 h; 75%		! "
			H
O	S	S
	O	O	O
	Ph		Ph
40	41		42

M

M

O				O
N	R1		Ph	N	R1
	Ph
	R2	DCM, 25 C		H	R2
	+
		13 kbar, 36-41%
	R3			H	R3 ! "
MeO OMe			MeO OMe
43	44			45

R1, R2, R3= H, Me, OMe, OSMT, OSMDBT

	O	R3		O	R3
R2				R2	H	R4
	+	R4	13 kbar, r.t., DCM
R1			31-96%	R1		R5
		R5			H		! "
MeO OMe				MeO OMe
46	R1= Et, R2= H	48			49
47	R1= Me, R2= H		R3, R4, R5= H, Me, Ph, OSBT

M

O

Diene

52/53

Yield (%)

R1

R

H

7 kbar 1 bar

7 kbar

1 bar

24

9/1

1/9

70

55

H

19/1

1/3

80

30

O

R

51

H

R1

R

52

+

O

OH

O

R

H

R1H

R1

R1H

R

24 R=H, R1=Me 50

R

R

H

51 R=Me, R1=H

H

H

R

R

H

R

H

H

54

53

M

Ph	NC	CN				Ph		Ph
						CN		CN
	+		DCM, 50 C				+
			10 kbar, 31-96%			CN		CN
R		R1			R	R1	R	R1	! "
55		56				57		58
		R= Me, Et, i-Pr		R1= Me, Et, i-Pr, t-Bu

O		R	O	R
			H
	+	8-12 kbar; DCM
		r.t. ; 47-96%	(CO)3Fe
(CO)3Fe				R1 ! "
		R1	H
59		60	61

R, R1= OAc, OSMT, OCOC6H3-3,5(NO2)2

M

M

M

$

C7F15		1.5 kbar, 50 C	C	F	15	C	F	15
			7			7
	+				+
N		29 h, 37%	N			N		! "
62	51		63			64

M

M

			H R						R	R
					50-65 C
		+	C					O	+	O
		OMe	O					OMe		OMe
		18b	65			66				67
	R1 R2		Eu(fod)	, 10 kbar, DCM						R1
										R2
+		C	3						O
			50 C, 20 h, 12−81 %
	OMe	O
									OMe
18b		68								endo/exo = 6/4, 3/7

R1 = H, Me

R2 = Me, Ph, 2-Fu, CO2Me, CH(Me)OSMDBT

M

RMe2SiO

H

RMe2SiO

CO2n-Bu RMe

SiO

CO

n-Bu

CO2n-Bu

2

2

+

C

O +

O

OMe

O

OMe

OMe

69

70

71

72

H	O									H
										H
C				OMe
										O OMe
O	O	+			20 kbar; DCM, 53 C				O
O						20 h; 70%				O
		O								O
	O									O
										O
	73			18b						74
		O	H			O		H
			C	O	OMe		C		H
			H					O
				H
								OBn H
			H
				O	H		H		O
			O
								H	O
				75				76

M
MeO2C O	R	R1		MeO2C O R1		MeO2C O R1
				R		R
	+				+
				R2		R2
	H	R2
OMe				OMe		OMe
77		78	79			80

M

M

M
M
MeO2C O	R	R1		MeO2C	O	R1	MeO2C O R1
						R	R
	+					R2	+
	H	R2					R2
OPh					OPh		OPh
81		78			82		83

M

M

M

M

O

O +

84

84

DCM 10 kbar

O	H
	O
	H
	O
	H
O	O
	H

PhMe

O		∆
85
		O	O	H		H	O	H
						O
			H		85	H	H
				O	PhMe, ∆	O		O
			86				87
						DCM	84
						10 kbar
	H	O	O	H		H	O	H
						O
		H	H			H	H
85	O			O	DCM	O		O
PhMe					10 kbar
∆, 12 h		H	H				H
	H	O	O	H		O	O	H

90

88

89

M

O			O
	CHBr	NaI, 9 kbar, DMF
	+	60 C, 17 h, 32%	! "
	CHBr
37	91		92

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