The Diels-Alder Reaction

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								R
+	R		H2O
	+	CD							H
									R

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S	S		O			O
HO			HO
		89 C			+
		6 h		S		S
	O		S		HO
						S
	73			74		75
Medium		74/75	Yield (%)		R	R
					HO
						76 R = Me
H2O		1:2	20
						77 R = OEt
H2O + α-CD			25
					O
H2O + β-CD		1:1.5	91

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O			O
N O		N	O
	H2O + b-CD	H
O			! "
	65−90 C	O H
	84%
78		79

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OR1

OR1

OR1

OR1

Pr4NIO4

H

H

O NH

O N

O N

+ O

N

0 C, 1 min

OH

O

O

O

R2

R2

R2

R2

80

81

82 (endo)

83 (exo)

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Ar	O			O	H			O	O	Ar
	Ar	30 C	Ar	H		O	Ar		N
O +
	N	C2D2Cl4				N	+	H
	O			O				H O
						Ar
								87 (exo)
84	85			86 (endo)
R	R	Ar	P	Ar			Ar	P	Ar
N	N					Ar				Ar
Zn
		Ar			Ar		P		P
N	N
		P		P			Ar		Ar
R	R	Ar		Ar				89
P			88				R = CH2CH2CO2Me
			R = Et
Host	Selectivity	krel (endo)a krel (exo)a					Ar =
none	exo + endo
88	exo			1000
89	endo	500

aRelative to rates in the absence of host at 30 C.

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	N (CH2)6		N
CO2Et	CO2Et		4 Cl
+	H
			! "
EtO2C	H
	CO2Et
	N	(CH2)6	N
		[CP 66]

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N	N
O	N	O
		O	O
OR
			N
( )7
			C6H4p-SO3
90 R = SO3Na
		SO3Na
91 R = β-maltose	92		93

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NHCO2(CH2)6NMe3Br			NHCO2(CH2)6NMe3Br
	COC6H4p(CH2)5Me		COC6H4p(CH2)5Me
	+			! "
	95
SO2C6H4p(CH2)5Me			SO2C6H4p(CH2)Me
94			96

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Me3N-(CH2)4-pC6H4-S			CO2(CH2)6NMe3Br
Me-(CH2)7-pC6H4-S		+ RO				pH = 7.0
	97	O	98 R = Me			130 C, 2h
			99 R = Bu
			100 R = (CH2)7Me
			Me3N-(CH2)4-pC6H4-S			CO2(CH2)6NMe3Br
Dienophile	101/102	Yield (%)	Me-(CH2)7-pC6H4-S			CO2R
98	1.4	63			101
					+
99	2.0	85
						CO2R
100	2.6	90	Me3N-(CH2)4-pC6H4-S
			Me-(CH2)7-pC6H4-S			CO2(CH2)6NMe3Br
					102

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		M
I Me3N-(CH2)6-S		H2O, 25t ˚C, 52 h
	+ 100
		95%
Me(CH2)7Me2Si
103	S	CO2(CH2)6NMe3X	S	CO2(CH2)7Me	! "
		+
	S	CO2(CH2)7Me	S	CO2(CH2)6NMe3X
	104	6.7 : 1		105

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HO-(CH2)4-pC6H4-S	Me2N-(CH2)6-S	CO2(CH2)6Br
Me-(CH2)7-pC6H4-S	Me(CH2)7Me2Si	RO2C
106	107	108
		R = Me, Bu, (CH2)7Me

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			O		O
				R
			O		O
1	109	110	111		52 R = H
					112 R = Me

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			C6H4-p-R
	+		H2O
		O	25	C
		2-Py
1		113 a: R = NO2
			b: R = CH2SO3Na
			c: R = (CH2NMe3)Br
			d: R = H

	C6H4-p-R		O
			2-Py
		+
H
			C6H4-p-R
O	2-Py
(endo )			(exo )

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		O	O
		H2O
	+		+
		OR
		r.t.	OR
		O OR
		A (endo)	B (exo)

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OH

H

N

Cl

114