The Diels-Alder Reaction

				M
M
#			(CF2-CF2)n-CF2-CF
#				O(CF2-CF-O)m-CF2-CF2-SO3H
#
#				CF3
#				Nafion-H (144)
#
#

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				O
R				O
		Nafion-H	A	R
O	O	DCM
		r.t., 3−10 h
				R
			B	O
				O
				H O
	( )n			O
		Nafion-H	A	( )n
				H
O	O	DCM
				H
		r.t., 3−10 h
				( )n
			B	O
				H O

R	Reaction	t (h)	endo/exo	Yield (%)
Me	A	7		80
Me	B	10	85:15	81
Ph	A	8		79
Ph	B	12	90:10	84

n	Reaction	t (h)	endo/exo	Yield (%)
1	A	4		68
1	B	4	96:4	68
2	A	3		92
2	B	4	95:5	89
3	A	4		94
3	B	4	80:20	91

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	M
			O	O			O
							O
	O	H			0 C, r.t.			R
			N	O
	+							H
					3−5 d		HO
	O	R	Ph
	OH						O	N
	145		146				endo

M

Bn		1. I2, DMF
N	+	−78	C, 1 h, 88%	H
		2. n-Bu4NI
O				O N	! "
147	1			Bn

endo/exo = 3:1

		M
Bn	Bn			H
I2	N		I
N				O N Bn I
O	O		I
147	148			I
				149
		H		n-Bu4N I

ON Bn

M

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	EGA		O	O-EGA	R	O	! "
O O
R			R			O
M
						( )n
	( )n +	R	O	−78 C, 3.5 h
						R
			O	15V, ClO4	, DCM		O
			150			O

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HSVM	+	2
1h, r.t.		! "
C60 +
C60		C60
151		152

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$

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	OH	O			O		OH	OH
		M			M	H
							+
		R			R		R	R
153		154			155		156	157

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M

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		O					O
						O
	Si	N Ph	Si	O
							N Ph
	O		O
				N Ph 10% TFA
		O
							O
		DCM, 25 C			99%
				O
		14 h
						MeO
	MeO		MeO			OMe
		OMe		OMe
		13 examples
M
		O
		H
		O				BnH COOH
					TFA
Bn	COO		Bn	COO		H N
					DCM
	NH2	AcOH, NaBH(AcO)3	H N			H	O
		48 h		O
			7 examples
M
		O			H O

Zeolite-Beta +

r.t., 32 h, 63%

H

various zeolites

		O
	+	OMe Al2O3	+	CO2Me
		50 C, 5 h
			CO2Me

endo/exo ratio and yield depend on alumina activity

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CHO

K10-Fe

3+

CHO

+ DCM, −24 C, 60 %

O
	K-10	O
+
	0 C, 5 h, 70%
O		O
	23 examples

O		O
O	US, DCM, −78 - 0 C	O
		H
	+	O
O	1−3 h, 91%
		H
	9 examples

	O	O
		O
	O
		US, 1. 45 C, 1 h
	+
		O
CO2Me	O	2. DDQ, 65%
		CO2Me
(−)-(S)		(−)-(S)

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		O
	+	US, 10 C, 1 h	+	COMe
		CH2Br2, 18%
		COMe
		95.1%		4.9%

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			O					O	R1
	O
R1		+	X	MW, HPL 80%				X	O
	O
				4min, 51−59%			O	R2
			O						X
	R2
									O
X = O, NPh			R1 = pMeO-C6H4 R2 = pMeO-C6H4, Me

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	M
		Ph			Ph
	N	N	Graphite, MW, IP = 30W N
			+
	N	N		1 10 min, 70 % H N
		Ph			Ph
			5 examples

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Cl	F	MW (600W), 3 min	F	Cl
			SO2Ph +
+	SO2Ph	neat, 95%		SO2Ph
F			Cl	F
			F	F

dienes: furan, 1,3-diphenylisobenzofuran

O

	O		O
+	MW, 160−187	C	O
	O
	p-xylene, 3 min, 92%
	O
O			O H

MW, 400−425 C +

neat, 15 min, 25% H

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O			OHO	O
CHO	O	hν (100 W)	O
				O
+		PhH, 2 h, 69%
Me	O

O

11 examples

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OMe

	O	DCM, florisil	O
O		r.t., 48 h, 44%	H
OMe	O		O
		1. hν (Rose Bengal)
		0 C, CHCl3	H	O	H
O	O SiMe3 2. ZnI2, 20 C
			O	O	OH
		20 h, 58%

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COR
X CN	hν (λ>280 nm)		X	CN
+				COR
	PhH, C6H12-Me2CO
	2−48 h, 18−29%
R = H, Me, Ph	X = Morpholino, S-t-Bu

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O	NHCO	Et	β-CD, H2O		H	NHCO2Et
	2				O	CO2Me
	CO2Me		85 C, 7 d, 32%

3examples

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R1	β-CD, H2O	R1
+	60 C	+	R
R			R1
	R

R = CN, CO2Et, CO2Bu, CO2Pr, COMe, CO2H, CO2C6H11

R1 = H, CO2Et, CO2H, Various solvents

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CH2OH	CH2OH	N	N
OOH	OO ( )5	O	O	( )5
OH	OH	N	H2O, 25 C	N N
O	+		O	O
OH			20 min	N
OH	OH
			SO3Na
				SO3Na

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							O
							OR2
R-S	S-R1					C8H17O			R-S	S-R1
				RS	SR1		O
		∆
S		−SO2					130 C, 2 h, 90%
O O									C8H17O2C	CO2R2
R = pC8H17-C6H4				R1 = (CH2)4NMe3Br R2 = (CH2)6NMe3Br

#

O		H
	H2O, CTAB	H O
+
	30 C, 3 h, 68%
		O
O

#

+	+	R
R	R
R = CN, CO2Me, CO2Bu	various surfactants; various solvents

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	OH		O	O
	+	tyrosinase	O	+ O
	O	r.t., CHCl3, 1 h		O
		pH 7.0, 24%	Me
	Me			Me
			O
		various examples	2	: 1

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	OMe		OHC	OMe
HO		Diels-Alderase	O	H
			O
		30 C, pH = 7, EtOH
	O O		Me	H
		2 h, 51%, ee 98%

M

	Nafion-H, DCM
	+	O
	r.t., 4 h, 95%	H O
	O O
	6 examples	endo/exo = 95:5

M

	O		1. HBF4, −45	C
	O	OEt
			10 h, DCM
	+
	R		2. TsOH, MeOH
			74%		OH
					O
					R
	6 examples				de = 75:1

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O	OH	OH
H	A, CD2Cl2
+	CHO;
	55 C, 48 h, 60 %
	NO2	NO2
	11 examples	A