The Diels-Alder Reaction

M

M M

		O
	O	H
	O	1 S
O	S	2
	LR, PhH,	H
	80 C, 1 h, 94%
		O
	O

O

O

135 (1,2-trans)

134

136 (1,2-cis)

O

H

O 1 S

2

HH		H	C, 7-14 h
		xylene, 140
	H
	O	O
137	(1,2-trans) (54%)		LR = Lawesson's Reagent
138	(1,2-cis) (81%)

M

M

			M
	R
	N	X
	N		R
			X
			N
	X	N	xylene, Rfx
			17−87%
		N
			N
	139		X
			R
	R = H, Me
	X = O, NBz
	N
	N		N
			xylene, Rfx
		N	75%
		N	N

140

M

		O
	+	PhMe, 100 C	O	O
		24 h, 79%
		O	O	O

141

M

M

		O
		O		H	O
				H
			O
O	O	O , PhMe			O
		Rfx, 2 d, 68%
	142		143		O
			DMF, Rfx,
			6 h, 85%
		Cu2O,quinoline, H2O,
		Rfx, 16 h + 24 h			O
		60%
					O
	145		144		O

M

M

M M M

					M
O			N	N			Py O
				Py O		N
			N		- N2
E						N	E
			N		E
			Py		Py
X				X			X
							Py
							- N
							N
E		Py			E		Py
X
O	N	N		PhMe, Rfx, 15 h			X
	+			78-89%
	N	N			O		146, X = O
148, X = O		Py					147, X = S
149, X = S					1. OH
E = CO2Me					2. H
					DDQ
			O	S	X = S		X
					DDQ	O

X = O

M

M

M

M

			R2 R3	o-Cl2C6H4 or PhMe		R
	R	R1	OH		O		R1
				R2
				or xylene
		O +		R3		O
	MeO			Rfx, 6−72 h
	150		151		152
						63−90%
	R = H, CN, COMe					R
				R2		H
	R1 = H, Me, CO2Me				O		R1
	R2, R3 = H, Me			R3

O

H

153

M

M

M

	R2				R2
	+	R*	DCM, MS 4A
			20−40 C, 18−20 h, 2−27%
							R*
	N	O			N	H
	R1				R1		O
	R1 = PhSO2, Me; R2 = Ph, Me				SO2
					N
				R* =
	6 dienes: 3-vinylindoles and 2-vinylindoles				H

R	O		H O
	DCM or PhMe, r.t.	R
+			H
	X		X
	4−5 h, 64−100%
	O		O

(S)

(both enantiomers R and S)

X = O, NH; R = Ph, p-MeOC6H4, o-MeOC6H4, 2,4-(MeO)2C6H3, 2-Naphthyl

M

t-Bu	O			t-Bu	O	H
		PhMe, 120	C, 30 h
	+
		90%
	O				O	OAc
t-Bu	AcO				t-Bu	H
	4 dienes

M

M

R2	E	R2
		E		R1	E
R1	R1
	PhMe, Rfx, 20 h		DDQ
	+
R	R	E		R	E
	E
R = Me, OMe, OTMS; R1 = OPh, p-MeC6H4;			overall yield: 40-92%
R2 = SBu, OSMT E = CO2Me

5 dienes, 3 acetylenic dienophiles

M

		OCH2CH2OH		( )n	( )n
O O		C60	O	TsOH
		( )n		C60 CHCl3−MeOH O	C60
( )n		xylene, Rfx, 36 h	O
		N2, 71−82%
n = 1, 2

M

Ts
PhMe, 60 C, 6 h	Ts
+
90%
SePh	SePh	O
7 acyclic and cyclic dienes

M

R

		R		R
	X R1 ∆	X
				X
	R2	R1	Et2O or PhH	R1
		R2	130−140 C, 6−7 h
			30−93%	R2

R = H, Me; R1 = H, Ph; R2 = Ph, CO2Me, 4-CF3C6H4; X = Se, Te

M

R	t-BuO2C
	O	O
t-BuO2C	R
	PhMe, 110 C, 6 h
+	16−54%
TMSO
	O Ar	O Ar
	TMSO

H

R = H, OMe; Ar = Ph, p-MeOC6H4

OSMDBT					O
R	COCl				R
N		C	MeOH, r.t.		N
+	THF, −78
					O
R = Me, Ph, p-MeOC6H4					20-50%

M

	OMe			H
	p-cymene, 200 C	DCM, CSA		O
N	+
PhO2S	8−96 h		1 h	N
O	OSMT			PhO2S
				O
	R
R = CO2Me,				R
				53−74%
	(CH2)3-CN

M

M

					R		O	CO2Me
H2N		O	CO2Me			PhH, Rfx
					+
					12 h, 68−99%			R1
					R1		NH
								2 R
R = H, Me, CO2Me
R1 = CN, COMe, CO2Me, SO2Ph
R-R1	=	O	N	O			CO2Me

Ph

BF3

R

OH

CO2Me

R

NH2

PhH, Rfx R1 = H BF3, 1 h 74−99%

MeO2C OH

R1

R

NH2

THF, TsOH R1 = H 25 C, 0.5 h

74−84%

MeO2C OH

R

O

M

O
DCM, 120 C		O	+
+
22 h, 68%		H	O Ph
O Ph	O		O H O
		Ph
O
		O
6 dienes; 4 acyloxyacroleins		2.6	1

M

M

	CO2Me		CO2Me
	+	THF, 40 C
		24%
	N		N
	Me		Me
	4 vinylindoles; 2 arynes
		% # & M

O	O	MCPBA	O
PhMe, 25	C		C60 O
C60 +	C60
12 h, 73%			O
O	O
		O	H
			or SiO2
	C60	O

O

M

				H		H
				H		H
	H	+	DCM	O	+	O
	H		−40 to 20 C, 0.5−48 h	O		O
	R
O				R		R
			75−93%	R1		R1
O						EtOAc, Rfx
	R1
						24 h, 75−82%
R = R1 = H, (S)S-SOTol				H		H
				H		H
				O	+	O
				O		O

M

NMe2	CO2Me				CO2Me
				MeO2C	CO2Me
	+
R	CO2Me
R = CO2Me, CN 16 dienophiles		xylene, r.t. or Rfx, 0.5−28 h, 10−95%

M

R	CO2Et			R	R
				CO2Et	SMT
+		PhH, 235−240 C			+
		14−24 h, 74−92%			CO2Et
	SMT			SMT
R = H, OMe

% # &

			R	R
O
R	CN	C, 7 d	O	O
	PhMe, 300
	+			+
O	32%		O	O
	R = Br
			CN H	CN H
R = H, Me, Cl, Br; 5 dienes
			86	14
M
O O				H
S	PhMe, 150 C, 18 h
O				H
	+			SO2

96%

O

7 dienes