The Diels-Alder Reaction

M

OAc

O

O

O

Cl

Cl

Cl

Cl Cl

Cl

AcO	O			OAc
					O
22	O	21		O
PhH, 110 C,		PhH, 25 C,
				O
24 h, 4−7%	O	24 h, 82%	O
26
13 h/50 C
and 19 h/80 C
	25
OAc		O
	+
O		O
		OAc
O		O
O
			CO2Me
		O	27
CO2-l-menthyl		Cl Cl			Cl Cl
		Cl	1. OH		Cl
		Cl			Cl
160 C, 8 h, 65%	Cl		2. H	Cl
		Cl			Cl
		CO2-l-menthyl			CO2H

2R-(−)

! "

	CH2O-l-menthyl	Cl	Cl		Cl	Cl
		Cl			Cl
			Cl	H		Cl
	160 C, 8 h, 83%	Cl			Cl
		Cl	CH2O-l-menthyl		Cl	CH2OH

2R-(−)

M

M

				H	O
	O	+		PhMe, 110 C, 65%	O
R*O O
						! "
					H
28			21	H
					OR*

R* = l-menthyl

R*O	R	O	R*O O O
	O
	28		29	R* = l-menthyl

M

M

M
				CHO	O	R
		+			Na2CO3, BHT, 70 C	CHO
					5−20 h, 100%
	O	R
				CH(OEt)2
	31					CH(OEt)2
				32		H2, Pd/C
						EtOAc
						100%
	CH(OEt)2				CH(OEt)2	O
TBDMSO	CHO			HO	CHO KOt-Bu, TMEDA	R
						CHO
	R	TBDMSCl			−55−23 C, 80−90%
		imidazole			R	CH(OEt)2
		80%			CHO
			TBDMSO		CHO
	SiO2/(CO2H)2
	DCM, 90−95%				R

R = Me, Et, Bu, n-C5H11, n-C7H15, n-C8H17

		R1 R2	CO2Me				R2
						R1
			+	xylene, Rfx
	R	S		2−96 h, 16−75%		R	CO2Me	! "
			CO2Me
		30					CO2Me

R, R1, R2 = H, Me, OMe, SMe, Ph

M

M

M

OH

CO2R*

MeO

O

DCM, AcOH, 95 C

LiAl(t-BuO)3H

MeO

CO2R*

+

MeO

40 min, 80%

Et3B

MeO

CO2R*

CO2R*

Ar

Ar

! "

34

33

Me

R* =

H

Ar = 3,4-(MeO)2C6H3

CO2Me

O	Br CHO				O	Br O
O	R				O	O
					O
R = H, Me		DCM, 78−90 C			O
		33−63%
	R	H			DCM, 90 C, 63%
		O	O
			O	Br
	DCM, 90 C		35		OMe
	63%	O			OMe
		O		DCM, 80 C
				60%
O	Br				O	Br
	O					OMe
O	O				O	OMe
	O
		R	25−100	C, 2−5 d	Br
O					O
	+					R
			83−100%
					O
						! "
	Br
	36

R = CN, COMe, CO2H, OCH2CH2Cl, OSiMePh2, p-Br-C6H4

M

M

M

	R3	H	R1
		ArS R3	ArS	R3
				H
	ArSCl	R2	R
				R1
		DCM, r.t., 2 h,
				R
		51−95%
	SnBu3			R2
	O	O
	R-R1= C O	C , R2 = H; R = CO2Me, R1 = R2 = H
		O	Ph O
	R1 = R2 = CO2Me, R = H; R-R1 = C		N C , R2 = H

Ar = Ph, o-NO2C6H4; R3 = H, Me, Ph, CO2Et

M

#

X

Z

S S

3738 X = Me3N+I−; Z = SiMe3 39 X = SiMe3; Z = MeEt2N+I−

M

		O
		N Ph		O
	NMe3I
					! "
	Bu4NF	O		N
	SiMe3	MeCN, 20	C		Ph
S	S			S
		89%
				O
	38	37

M

	R		R
	O	O
O	N	O	N
	R1		SO2Ph
	40		41

R = H, Me; R1 = CO2i-Bu

$ $

M

M

	MeO2C
	MeO2C	N
		CO2i-Bu
	DMAD
	PhCl, Rfx,
	18 h, 88%		SOPh
	O
N	MeCN,PhCl, ∆, O	N	PhCl, Rfx
CO2i-Bu	6 h, 84%	CO2i-Bu 144 h, 85%
	40
	H	CO2Et
	PhCl, Rfx
	20 h, 75%
EtO2C
	+
	N	EtO2C	N
	CO2i-Bu
			CO2i-Bu

O

R N O

R1

42

N

CO2i-Bu

R = (CH2)2Cl, Ph, p-ClC6H4, m-ClC6H4, o-MeC6H4, m-MeC6H4, p-MeC6H4, o-BrC6H4

R1 = H, Me

M

M

M

R1

O

O

CO2Me

N

CO2Me

R

R1

CO2Me

180 C, 1 h

R1

O

CO2Me

56−85%

O

COMe

O

CO2Me

O

N

O

N

R

R

H

CO2Me

O

+

R

N O

+

xylene, 130−160

C

R1

xylene, 60−130 C

R1

18 h, 0−40%

1 h, 63−90%

O

42

R1

O

O

O

R1 = H, Me; R = Ph

N

COMe

N

CO2Me

R

R

O

180 C, 1 h

N

Ph

75−79%

O

R1

H

O

O

O

N

N

Ph

H

R

O

M

O

O

R1

O

O

S

R1

S

DCM or PhH, 60−160 C

+

2−180 h, 26−97%

S

R

S

R

! "

O

O

O

O

43

O

Ph O

R = OEt, SPh, TMS, OAc, CO2Me, COMe, Ph; R1 = H; R-R1 = −(CH2)4−,

C

N

C

M
	O	O		O
			H	Ph
	O	N Ph		N
		, X = H		O
N	H	O
				H
X		PhBr, ∆, 5 h, 58%	N
∆			H
				O
	O	O , X = H
N	H	PhBr, ∆, 2.5 h, 45%		O
X			N
44			H
		CO2Me		CO2Me
		, X = CO2Me		CO2Me
		MeO2C

PhBr, ∆, 26 h, 54%	N
	CO2Me

			C60
Cl	PhMe, NaI, 18-crown-6		15
Cl	Rfx, 3 d, 23%	MeO2C	C60
MeO2C			S
S
45			46

	Br	C60
	Br PhMe, NaI, Rfx	15
S	18-crown-6, 24 h, 43%	S
47		48

! "

CO2Me

S

C60

! "

S

M

			M
OHex			OHex
O2S	SO2	∆
OHex			OHex
49			50
		C60
		15
	Cl3C6H3, Rfx, 20 h
	OHex		OHex
C60		C60	C60
	OHex		OHex
			n
	n = 0−5
Hex = C6H11		51

M

H	H
H	H
	52
OMe	O
AcHN	H2N
OMe	O