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Казанский национальный исследовательский технологический университет

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Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 1 / 0547 617

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							H	H
O	+	O		O	∆, 14 h	O	O	O
O	+	O		O	81%	O	O	O
					81%
(1)							H	H
(1)
(44)			(44a)
							44a, 45°C,	13 kbar, 150 h
								yield: 49%
		H			H		H	H
O		O	O		O	O	O	O
		H			H		H	H

SCHEME 10. Ribbon-type oligomers and polymers via repetitive Diels Alder reactions

Reference

577

		R
+	O	O
(2)		R
		R
(45)		(46)
		R=n-Hexyl
45 +	O	7.5 kbar
		50 °C, 2d

O	O	E		E


			8.6 kbar
			8.6 kbar
(3)
	(48)	E =CO2 Me
	(48)

578

		R					R
7.5 kbar		O	O			O	O
40 °C, 2 d		O	O			O	O
40 °C, 2 d
		R		(47)			R
				(47)			n
							n
H			H				Reference
H			H				96
							96
O			O	+	anti
O			O		11.1%
					11.1%
H		syn	H
H		45.5%	H
		45.5%
	E	E			E
					E		E
O		O
		O

		+ O		O	O		O
					E		E
					E	n
						n
	(49)				(50)		Reference
							97

SCHEME 10. (continued)

12. The effect of pressure on reactions of dienes and polyenes

579

				O
					O
(1)	O +				+
(1)	O +	CN			+
		CN			CN
					CN
(51a)				endo,exo CN	endo,exo
10 kbar, 80 °C, 10 h			Product ratio pressure-independent (6−10 kbar)
conversion of			but temperature-dependent (70−140 °C)
51a :91%
1 bar, 140 °C, 12 h
conversion of 51a :100%
	X	O
		O
(2)	O +			E
X = H:	51a		E
X = OH:	51b		E
X = OH:	51b	(52)
X = OMe: 51c		(52)
X = OMe: 51c
X = Cl:	51d

Reference

3 kbar, 100−110 ˚C,

11−12 h

yields:44−88%

O		X
O		O
	X			X
	X			O
	+			+	O
					O
	E		E		E
O		O
(53)	E	(54)	E	(55)	E
					Reference
120−130 °C, 1−7 d		O		X	99
120−130 °C, 1−7 d				X
E				O
E				O
−	O	X
E		X
E

E = CO2 Me

(56)

(57)

SCHEME 11. Diels Alder reactions of tropones as dienes

580

Frank-Gerrit Klarner¨ and Matthias K. Diedrich

10 kbar, 100 °C, 10 h

(3)

51a

60%

25%

Reference

100

51a +

10 kbar, 100 °C, 10 h

29%

(4)

51a

3 kbar, 130 °C, 10 h

R1 =R2 =R3 =H

R1 =OCH3 , R2 =R3 =H

R1 =H, R2 =R3 =OCH3

Reference

101

+secondary products

no reaction at 1bar, 130 °C

SCHEME 11. (continued)

the

most

prominent examples

is the synthesis of a

cantharadine precursor by

the cycloaddition of furan to the substituted maleic anhydride shown in Scheme 13, entry 1, which occurs only at high pressure or when catalyzed by LiClO4. Other examples of pressure-induced Diels Alder reactions with ﬁveand six-membered heterocyclic dienes such as furans, pyrroles, oxazoles, isopyrazoles, phospholes, ˛- pyrones and pyridones are depicted in Scheme 13. High pressure is here not only useful for synthetic purposes, but also provides important information concerning the course of reaction. One example is the addition of cyanoacetylene to furan and furanobenzocyclophane 63 (Scheme 13: entries 4 and 5) leading to the (2:1) adducts 61 and 66, respectively, as the major products at 160 °C and atmospheric pressure. In analogy to the trimerization of cyanoacetylene (Scheme 5: entry 3) and the addition of

12. The effect of pressure on reactions of dienes and polyenes

581

(5)

C6 0

+ X	3 kbar, 80 − 130 °C	O
Y		X	O
			O

Br		Y
		Y
Br		O
Br
+ X	3 kbar, 80 − 130 °C	O		Reference
Y			Br	Reference
Y		X		102



O		Y
		Y
	O

	X		R	R=CN, Ph
	:	N-Ar,		R=CN, Ph
	Y		,
		O
		SCHEME 11. (continued)
	X		X
			X
			O
	O			X	Y
				X	Y
Y				H	H
Y				OMe	H
3 kbar, 100 °C, 36 h				Br	H
3 kbar, 100 °C, 36 h			C6 0	H	OAc
yield: 52−73%				H	OAc
yield: 52−73%		Y		H	OMe
		Y		H	OMe
				+
3 kbar, 110 °C, 36 h			C6 0
			C6 0		14.5%
			52%		14.5%
	O
1. ( )		( )n	O(CH2 )2 OH
1. ( )	O	( )n
n	O
3 kbar, 130 °C, 24 h				( )n	n =1, 2
2. TsOH, CHCl3				( )n	n =1, 2
2. TsOH, CHCl3
yield: 85%
or	O		OH		C6 0
( )n		( )n	O

3 kbar, 130 °C, 24 h yield: 81%

Reference

104

Reference

105

C6 0

Reference

106

SCHEME 12. Diels Alder reactions with fullerenes as dienophiles

582

(a) Furans
		O	O				O
		O						O
								O
					S	+		O
(1)	O + S	O				+
(1)
					O			O
								O
		O	O		O			S
	4−15 kbar, 20 °C,				O			S
	4−15 kbar, 20 °C,							(pressure
	40−100% conversion				1	:	4	(pressure
								independent)
	5 M LiClO4 , Et2 O,
	20 °C, 10 h, yield:70%				1	:	5.7
	O			O	O			O
					O
			MeO		O
+ X	O	8 kbar, 6 d, 20 °C			O		H2 ,
							H2 ,
							Pd/C
			MeO				Pd/C	OMe
			MeO					OMe
					O			MeO
	O				X			X
X:CH2 CH2 , CHMeCH2 , CHMeCHMe, CH2
yields:18−28%

Reference

107

O Reference

108

		O		O	O
				O
						MeO
	Cl		MeO			MeO
	Cl	10 kbar, 27 h, 25 °C				−HCl
+					O

		O
	Cl		MeO		Cl	MeO
			MeO		Cl	MeO
		O			O
MeO		O			Cl

(2)O

	MeO	Ph					O	MeO
		Ph						MeO
					MeO			O
		+	O	8 kbar, 48 h, 55 °C				− CO
		+	O	R	= Ph, Me			rearr.
				R	= Ph, Me			rearr.
		R			MeO		Ph	MeO
							Ph
							R
					O			O
								O
						9 kbar, 20 h, 20 °C		MeO
					+	9 kbar, 20 h, 20 °C
					+		1bar, 26−52 °C
							1bar, 26−52 °C	MeO
								MeO
					O	E	= 25.4 kcal mol−1
					O	A
						A = 1.86 . 1015 S−1		O
				O	O		O
		OAc					O
		OAc			E			E
		11kbar, 9 d, 20 °C			E
	O +				+
(3)								+
(3)								+
					E		E
	E	E					E	O
	E	E						O
	E = CO2 Et				OAc		OAc
				endo:36%

exo: 49%

byproducts

SCHEME 13. Diels Alder reactions with heterocyclic dienes

86.5%

OAc

Reference

109

Reference

110

Reference

111

(continued)

583

					O	O		O
						O
				O			+
							+
			7 kbar, 38 h,						O
		O		25 °C		CN		CN
						CN		CN
(4)	O +					(59)		(60)
(4)	O +					22	:	78
						22	:	78
	CN							O	Reference
			CN			O		O	112
			CN			O			112
		(58)		CN					CN
			12 kbar, 24 h,				+
				40 °C			CN
						CN	NC (62)	+ (59)	+ (60)
				(61)			NC (62)	+ (59)	+ (60)
				10		:	2	: 13	: 46
			NC	NC			CN
			NC	NC
			NC				NC		CN
			NC						O
									O
	O	8.5 kbar, 60 °C	O		O
(5)			O	+			+


		CN
			(64)			(65)		(66)
	(63)		39	:		58	:	3
						CN
									Reference
									112
						CN
						(67)

584

SCHEME 13. (continued)

(6)	+
63

		1bar, 160 °C, 22h			9 kbar, 20 °C, 2 d	Reference
		conversion of 63 50%			1bar, 20 °C, τ 1/2 = 20 h	112
		conversion of 63 50%			1bar, 20 °C, τ 1/2 = 20 h
		NC	CN		CN
		NC	CN	NC	NC	CN
			NC		NC	CN


NC	CN	NC
	O	O	O		O	O
	O	O	O			O

(68) 20%

(69) 1%

(70) 18%

(71) 14%

(72) 86%

5 M LiClO4 , Et2 O, 24 °C, 3 h: 53%(only product) 8.5 kbar, 60 °C, 2 d:

SCHEME 13. (continued)

585

					O		O
(7)	X + O2 S			O	O2 S	X +		X + X
X					O2 S			X
E						X		X
E			1bar,	120 °C, 12 h:	−	X	61%	X
			1bar,	120 °C, 12 h:	−		61%
			1bar,	150 °C, 3 h:	−		63%
E			12 kbar, 28 °C, 48 h:		81%		−
E
		E	1bar,	120 °C, 1h:			62%
			1bar,	120 °C, 1h:			62%
			4 kbar, 28 °C, 24 h:				97%
			12 kbar, 28 °C, 48 h:		53%
					(1:2 adducta)

(b)Pyrroles

(8)N COR +

R= Ph, Me, Et, OBz

(9)N E

R= Ph, Me

E = CO2 CH3

			COR
O			N
N	Ph	14 kbar, 0 − 50 °C		O
		14 kbar, 0 − 50 °C

				N	Ph
O			endo / exo
		X	endo / exo	O
		X		O
		Y	45−90% yield
		Y		E
	SO2 Ph			N
	SO2 Ph
+			RS
+		E	12 kbar, 25 − 50 °C, 16 h		X
			80% yield	Y
		O		Y
		O	mixture of
			mixture of
			endo / exo
		N	Ph

O
	X +	X
		O
29%	X	X
	X	−
		−
−		10%
−	SO2	−
	SO2	Reference
	a	Reference
	a	113
29%		113
29%
3%
	O	E
	O
		E
		SO2
		Reference
		114

Reference

115, 116

586

SCHEME 13. (continued)

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