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Казанский национальный исследовательский технологический университет

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Химия

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The Diels-Alder Reaction

.pdf

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15.08.2013

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M
O	N	Z	Z = NCHMe2,SO2
	N	Z	X, Y = H, F, Cl
			X, Y = H, F, Cl
X O
	N
	N	21
Y	N	21
Y	N

CO2Et

H2O, 22−45 C,
24 h, 60−90%		X

X = H Y = Cl
X = Y = F
X = Y = Cl

		O		CO2Et
			CO2Et	O
thermal	X			CO2Et
X = H	X	CO2Et
X = H		CO2Et
Y = Cl
		Y		Cl
		23
O				O
CO2Et				CO2Et
CO2Et		Pt/H	X	CO2Et
			X

Y				Y
23				24

H2O

BnNH3 Cl + HCHO

[BnNH=CH2]Cl

H2O

T(˚C)

t (h)

Yield (%)

! "

CHO	+	MeNH3	Cl	H2O-EtOH 1:1	CH	Cl
	+	MeNH3	Cl	70 C, 30 h, 66%	NHMe	Cl
				70 C, 30 h, 66%

MeN	H2, Pt/C	MeN
	60%
dihydrocannivonine

H2O

BnNH3 Cl + HCHO

[BnNH=CH2]Cl

H2O, r.t.

Ln(OTf)3, 10−12 h

Yield (%)

catalyzed uncatalyzed

H2O

BnNH3 Cl

+ RCHO

[BnNH=CHR]Cl

H2O, r.t.

Ln(OTf)3, 12−20 h

(exo)

(endo)

Yield (%)

endo/exo

catalyzed

uncatalyzed

Me(CH2)4

74:26

Me(CH2)4

73:27

Me(CH2)4 Yb

72:28

80:20

99:1

H2O, r.t., 48 h

N Bn

Nd(OTf)3, 44%

[BnNH3]Cl +

HOH2C

O OH		HO	OH			HO
		HO					OH
				HO

CHO
CHO	H2O, r.t., 60 h			HO
OH	H2O, r.t., 60 h		O OH	HO			O OH
		N Bn	O OH		N
	Nd(OTf)3	N Bn		H	N	H
					H

			O	O
[BnNH=CHCOR]Cl +		H2O, r.t.	R +	R
[BnNH=CHCOR]Cl +			R +	R
			N	N
26			Me	Me
26
			(exo)	(endo)
R	t (h)	exo/endo	Yield (%)
Ph	22	81:19	82
Me	20	78:22	67

! "

	OSiMe	Ar
	Ph	N
	OMe
	MeCN, Yb(OTf)3,
Ar	0 C, 92%	O
N		O
N
C		H
H Ph		H

	H2O/EtOH/PhH,	N Ph
	Yb(OTf)3, 90%	N Ph
	Yb(OTf)3, 90%	Ar
		Ar
	Ar = p-Cl-C6H4

$ ! "

O			H	OH			H	OH
	H2O		H				H
	H2O	O			O +			O
+		O			O +			O
H CO2H		CO2H		O				O
			H				H
	27			28				29



#

					H	OH
	cat.				H
O	cat.	O cat.					O
O
						O
		H			H	O
O OH	O	H			H
30	O	O			28
30					28

# #

# # M

# ! "

# $

# #

25 C

R = NO2

(endo)

(exo)

! "

# M

$		$

M
O		H2O			O
+		H2O		+

		r.t.
		r.t.
			O
			(endo)		(exo)
catalyst	t (h)	endo /exo Yield (%)
InCl3	4	90:10		87
MeReO3	16	99:1		91

		M

				O	O
		Y	3−11 Kbar		O
	+	Y	3−11 Kbar		+
X	+		30−33 C, 24 h		+
X	O		30−33 C, 24 h	X		Y
				Y	X
				(endo)	(exo)

M M

+	CO2Et		r.t., 5 h
+
					CO2Et
5.0M LP-DE endo/exo = 89:11, yield 93%
H2O		endo/exo = 80:20, yield 73%
RO					O
		CO2Et
N	+			HN
N	+			HN
OR					RO
OR						CO2Me
5.0M LP-DE		r.t., 5 h, endo/exo = 75:25, yield 80%
PhH	60 C, 72 h, endo/exo = 8:92, yield 74%
		O		O		O
		O				O
O +	S	O	r.t.			O +
			r.t.
				S

		O				O
						O

					A
5.0M LP-DE			9.5 h, A/B = 85:15, yield 70%
DCM		6 h, 15 kbar, A/B = 85:15, yield 100%

O O

		M
			O	O
		5.0M LP-DE		O
		5.0M LP-DE		+
		r.t., 10 h, 74%		+
	O	r.t., 10 h, 74%
	O	O		O
		O

+		A		B

A/B = 6:1

O
Et2O
100%	O
	O
	O

O	O			O
O
		H	+	H
		H		H
		A		B

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