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Казанский национальный исследовательский технологический университет

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The Diels-Alder Reaction

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M
M
											1
	13	12									CO2R
		12				13				3	2
						13				3	2
						12
	11		10		1	H	9		6	H
					RO2C	H	9		6	H
						2 11	8	+ 7
											4
											4
		9	8			10				5	13
1					3	5	7	8		10	12
1	3	5			3		7				12
RO2C	3	5		7		4 H 6			9	H	11
RO2C	4			7		4 H 6			9	H	11
	4
	2		6
	2					A				B
						A				B
	R = H	H2O		100 C	A = 11%	B = 89%
	R = Et	H2O		100 C	A = 40%	B = 60%
	R = Et	PhMe		165 C	A = 75%	B = 25%

			O
			N	CO2R	RO2C	N
+			N			N
+	O		O				O
	O		O		+
			RO2C
			RO2C
RO2C		N	N				N
		N					N
			O
			O	CO2R		O	CO2R
			A			B

R = Bn	H2O/EtOH	-10 C	A/B	= 96:4	Yield 100%
R = Bn	PhMe	0 C	A/B = 93.5:6.5		Yield 100%

			N	Ph
		O	O
O	+	O	H2O
O	+	N	66%	O
		N
O		Ph
O		Ph	O
			O

three dienophiles

MeO	MeO

MeO	MeO	H
	MeO

H3N	50% EtOH-H2O		N
	+ HCHO	C, 23 h
Cl	110	C, 23 h
Cl
MeO			MeO
			MeO

O	CH2			O
C	CH2	+	H2O	O
C			H2O	O
O				O
O			r.t., 99%
			r.t., 99%
			CH2 O	CH2
			(endo)	(exo)

exo /endo = 79:21

		OMOM		OMOM			OMOM
		OMOM					H
		Bu4NIO4, H2O		H			H
		Bu4NIO4, H2O		+	O	N	A/B = 5:1
O	NH	O	N	+			A/B = 5:1
		O	N
		0 C, 1min, 83%	O			O
	OH		O			O
	OH

	Et	Et
Et	Et	Et
Et
7 examples	A	B

	+	CHO	H2O
	+	CHO	C, 24 h		CHO		CHO
		20	C, 24 h		CHO		CHO
H	OH		82%	H	OH	H	OH
	CH2OH				CH2OH		CH2OH
					65%		35%
					H		H
					H		OH
					OH	H	OH
				H		H	O
				H	O		O
				HO	O
				HO			OH
							OH

O		O		O	O
O		O		O
O	N	O	i-PrOH-H2O			O
+		O	0 C, 100%	HO		O
O				HO
O				O	N
OH			de = 95%	O	N	O
			de = 95%			O

RCHO + ArNH2

+ MeO

H2O-MeOH

OSMT

HBF4, − 40 C

0.5 h, 58−95%

R = Ph, p-MeC6H4, p-NO2C6H4, c-C6H11, BnCH2, i-Pr, 2-Furyl

Ar, = Ph, p-MeOC6H4

H2O, Nd(OTf)3

+ CH2O +

CO2Me

r.t., 12−20 h, 96−98%

H2N

CO2Me

( )n

H2O, InCl3

( )n

r.t., 4 h, 86−99%

R = H, Me, OMe

n = 1, 2

COR

13 examples

! " M

O
THF-H2O	O
+
Sc(OTf)3, r.t., 93%
O	O

100%

							R1
	R1				R1
	R1				R2	O
	O				R2
R2	O		H2O, Bi(OTf)3				O
	+					+
			r.t.,−100 C, 2.5−18 h			+
		COOH	r.t.,−100 C, 2.5−18 h			COOH	HO
	H	COOH	8-85%			COOH	HO
			8-85%				O
					A		B
R1, R2 = H, Me A/B = 43−99%: 57−1%				A (cis/trans) = 40−64%:60−36%

MeO2C		MeO2C		MeO2C
	O	O
		O
	N	5M LiClO4/Et2O
	N	N			N
		100 C, 36 h, 80%			N
	O	O	O			O
	O	O	O	O
		O

	Br	O	O
	Br	Br	O		Br	O
		Br				O

M M

TBDMSO	R	5.0M LiClO4/Et2O	O	R = CO2Me endo/exo = 75:25
	R	5.0M LiClO4/Et2O		R = CO2Me endo/exo = 75:25
	+
	+	r.t., 3−5 h, 80% HN
	N	r.t., 3−5 h, 80% HN		R R = CN	endo/exo = 23:77

TBDMSO

OSMDBT

8examples

M M

		H
5.0M LiClO4/Et2O		H H
r.t., 4 h,		H H
r.t., 4 h,
10 mol% CSA, 64%		H
O	O	O
		O

3 examples

	R1		O O		R1	O
R2		R	O O	4.0M LiClO4/Et2O	R2	R4
R2	+	R	4	4.0M LiClO4/Et2O	R2	O
	+		4	CSA, r.t., 1 h, 71−90%		O
				CSA, r.t., 1 h, 71−90%
R3		R			R3	R5
		5

R1-R5 = H, Me

O			O H
+	1.0M LiClO4/Et2O
+	300 MPa, 20	C
	300 MPa, 20	C
	5 h, 69%		H
O			O

5 examples

	OMe
CHO	+	0.5M LiClO4/Et2O	H O
	+	HCl/THF		O
HNBoc	OSMDBT	HCl/THF	H	O
HNBoc	OSMDBT	r.t., 11 h, 74%	H
			HNBoc
7 examples

OH					OH
HO	R3		anodic oxidation	O	R3
HO	R3		anodic oxidation		R3
+
+			LiClO4-MeNO2
CO2Et	R2		LiClO4-MeNO2		R2
CO2Et	R2		r.t., 16 h, 92−98%		R2
R1			r.t., 16 h, 92−98%		EtO2C
R1					R1
R1, R2, R3 = H, Me		15 examples

+	CO2Me	LiClO4 (4 mol%)		+
	CO2Me	DCM, 22 C
		DCM, 22 C
		16 h, 97%		CO2Me
			CO2Me
		82%		18%

			O		O
	O	O		N N
	O		Ph	(R)	Ph
+		N O		(R)			endo/exo = 95:5
						O N
			Mg(ClO4)2, DCM/H2O			O N
			Mg(ClO4)2, DCM/H2O			(R)	O
			−80 C, 48 h, ee 73%			O	O

MeO		MeO		CHO 14
CHO	4.0M LiNTf2/Me2CO			CHO 14
CHO	4.0M LiNTf2/Me2CO
+				H
+	40 C, 22 h, 80%			H
O	40 C, 22 h, 80%			O COOH
O			H	O COOH
H			H
COOH
7 examples	C(14)b-H/C(14)a-H = 3.6

	O	O
	ethylene glycol
	+	C, 6 h, 100%
	150	C, 6 h, 100%
	HO	H
	HO	HO
		HO
	Ph	Ph

7examples

		COR	MeO2C	CO2Me
			MeO2C	CO2Me	CO2Me
R			[BMIM]PF6
R		[BMIM]BF4	[BMIM]PF6		CO2Me
O	BF3 OEt2 (ZnI2)		80 C, 2 h, 98%		CO2Me
O		20 C, 2−6 h
		20 C, 2−6 h
R = OEt, Me		90−98%

R1	CN			R1
R2	CN	303-373 C		R2	CN
	+
R3	+	0.5−2 h, 88−100% R3
R3		0.5−2 h, 88−100% R3
R4				R4
R1, R4 = H, Ph R2, R3 = H, Me			12 examples

]

^ ^

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