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Казанский национальный исследовательский технологический университет

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Химия

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The Diels-Alder Reaction

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i-BuO2C

OEt

COO

EtO P

COO

N-methylmorpholine R

DCM

Wang resin

R1, R2 = Bn, i-Pr

1. r.t., 30−72 h

R3 O

COCl

DCM

2. TFA

COOH

1. r.t.

COOH

60−148 h R1

COO

DCM

2. TFA

		+	BnNH2	+ BnNC	E1		E1, E2 = H, CO2Et, CONHBn
R		+	BnNH2	+ BnNC	+		E1, E2 = H, CO2Et, CONHBn
R	O	CHO			E2	COOH
	O				E2	COOH
	17		18	19		20
	R = H, Me		r.t., 36 h		R			O	R E1
						E1		O

			MeOH				H
			72−89%	H	O	E2	N		E2
				H		E2	N		E2
				N			Bn	N	O
				N	N	O	O	N	O
				Bn	N	O	O	Bn
				O	Bn			Bn
				O	Bn			22
								22

21	isomer ratio = 86−92/14−8

			1. MeOH, DCM			O	R	E1
O			1. MeOH, DCM		H		R	E1
O			2. TFA
	NH2	+ 17 + 19 + 20	2. TFA					E2
N	NH2	+ 17 + 19 + 20	88−95%	Bn	N			E2
				Bn		N		O
H						N		O
H						O
23								NH2
	R2					24 O
1. TMOF	R2				isomer ratio
1. TMOF		(R1, R2 = H, Me)			77;91/23;9
2. NaBH4					77;91/23;9
2. NaBH4
R1	O	CHO
	25			R2	O	R1
				R2		R1
O	H	R2				COOH
O	H	O	O O
	N	O	O O	H	N O
N	N	O R1	Py, r.t.	H	N O
N		O R1	Py, r.t.	N
				N

CF3SO3H

(CH2)4

DCM

OSO2CF3

Et Et

(CH2)4 Si

31−97%

18−99%

N R

R1, R2, R3 = H, Me, Et, Ar

! " $

RCH2C

Cat., DCM

MeAlCl2, DCM

45 C, 24 h

−35 C, 18 h

1. Me3Al, DCM

R2NH2, DCM

r.t. 0.5 h.

r.t., 12h

2. Et3N, DCM

60 C, 24 h

R = (CH2)4Me, CH2OH, OCH2Ph, NMeCbz

= H, Me

R2 = Me, (CH2)nPh n = 1, 2, 3

	O
	R		O	R1MgX		O
	Cl		O	R1MgX		O
O	N	O	N	H+	O	N
			R	H+		R
						R1
						35

N R

p-Me-C6H4 m-MeO-C6H4 p-Me-C6H4

p-Me-C6H4 p-Me-C6H4 p-Me-C6H4

	O
	N	R	Y	65 C, 12h
	N	R	Y	THF
	R1		Y	THF
	Y
O	Y
O
Dienophile			Yield (%)
	NPMa		52
	NPMa		61
(EtOCON=)2			83

a NPM = N-phenylmaleimide.

					O
O					O
O				1. US
	+			1. US		O	A; B; C
	+	R1		2. DDQ		O	A; B; C
	O	R1	R3	2. DDQ
		R2	R3	R1
				R1	R3	R1, R2, R3 = see Table 4.8
	37	38		R2	R3	R1, R2, R3 = see Table 4.8
	O			O		O
	O			O		O
		O		O		O
					HO	R1
	R			O	R	R1
A	R = Me			B	C R = R1 = Me
	R = CO2Me					R = Me, R1 = OH
	R = CH2OH
	R = H

M
M

	O				O
	O			O				O		O
	O			O				O		O
	O		1. US
		+ R1	1. US				+
	O	+ R1	2. DDQ			O	+			O
		R2	R3
	37	38			D				E










		! "

M M

	$
	$
	$

NMe2

r.t.

NHMe2

OH O

NMe2

- NHMe2

NMe2

M
		N	CN	O
	CO2Me	NMe2		O
	CO2Me	NMe2		NMe2
				NMe2
N	CO2Me	60% A	N
NMe2		60% A	N
NMe2		H	B	O
	99%		B	O
	99%		50%	O
				O
	G	N	C
N CO2Me 47%		N	80%	N
NMe2		Me2		N
NMe2		Me2		O
		44	D	O
	F 95%		D
	F 95%		67%	O
	CO2Me	35% E
	CO2Me
N	CO2Me		N	N
NMe2		N	COMe	O
		N	COMe

NMe2

A = Acrylonitrile; B = Benzoquinone; C = Naphthoquinone; D = 5,8-Quinolinequinone; E = Methyl vinyl ketone; F = Dimethyl acetylene dicarboxylate; G = Methyl acrylate;

H = Dimethyl fumarate

M M

+	O	O	+	O
		O		O

H	R	R		R
		R		R



! "
! "
! "

					Ph
			N
			N		N	C6H4-p-OMe
			Et
			140 C, 7 min			NO2
						NO2

			285 W, 53%		Ph			NO2	Ph
S								NO2	N
S							N
			NO2 N				N
NO	2	S	NO2 N	N N		R	Ph
N	2			N N		R	Ph		N
N		13 C, 5 min		Et			140 C, 10 m		N
N N		13 C, 5 min		Et			140 C, 10 m		N N R
N N		240 W, 84%					285 W, 32%		N N R
Et		- NHMe2							Et
		- NHMe2							Et
			R =p-MeO-C6H4, NMe2						R =p-MeO-C6H4

M M

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