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Казанский национальный исследовательский технологический университет

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The Diels-Alder Reaction

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15.08.2013

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	O			S	O
		20 kbar, DCM, 100	C	S
S +	O	20 kbar, DCM, 100	C		O
S +	O	3 h, 47%			! "
		3 h, 47%			! "
	O				H O
	O				H

139b

					O	O
					O
						O
					HHO
O			O		O
O					MeCN
			O		MeCN			O	O
			O		O r.t.		O		O
					O r.t.
								C	NH
		H	O				90	C	NH
			O		O
							NH		H
	141

								H	O
								H	O
				O			O
		H2, Pd/C,			O
		H2, Pd/C,
			99%	O	139a			O
								O
O			O	O			25 C		H
O				O					H
			O	140					O
				8 kbar, 4 d, 97%				O	NH
		H	O					O	NH
			O

		O		O		O	O	O
				O			O	O
O	+		DCM, 15 kbar			O	+	O
O		O
			60 h


R		O		R	H	O	R	H O
		O			H
142	140				143			144



			M		M

AcO	O	HO	O	AcO
				CO2Me
	O		O
	H		H	CO2Me
	H		H
	145		146	147

	O			OMe
	OMe		5 kbar, 72 h
	+		5 kbar, 72 h	O	H H
	+		80%	O	H H
O			80%	H
O	H	H		H
				O	H
148	(−) 149			150
	OH			OH
	H			H
	O	H	O	H
		H		H
	(+) 151			(+) 152

! "

M
					R
	R1				O	H
	R O		10 kBar, MeCN-THF		O

		R1
	X	R1		C, 20-42 h
	X	60-70		C, 20-42 h	R1	X
					R1	X
					R1
153					154

		OH				OAc
			OH			OAc
			OH		H
	H				H
	H
		OH	H H		OH	H H
		OH	H H
	O HO				O HO
	O HO					OH
			OH			OH
			OH
		155			156
						R
	O	R		19 kbar, DMC	H	O
	O	R		19 kbar, DMC		CO2Me
					O	CO2Me
O				17 h, 45%	O	H
				17 h, 45%		O
					O H	O
O	O	CO2Me			O H
	O	CO2Me
157 a, R = SBn						158
	b, R = SPh

	Ph	Ph		O
Ph Si	Ph	Si Ph	O	H
	Ph	Si Ph		H
				H
159		160		161

		H		H		H
	H			H		H
O	H		O	H	O	H
O				H		H

	O			O		O
				O		O
	162			163		164

O	O		Yb(tfc)3, 12 kbar			OBn MeOLi		CO2Me
		Bn		O				CO2Me
				O
O	+
O	+		r.t., 3 d, 91%	O	H		HO	OBn	! "
					H		HO	OBn	! "

					H
165	166				167			168



! "
! "
! "
! "
! "


OAc				O
OAc
O	OR*	13 kbar, 25 C	O	OAc
	+	13 kbar, 25 C	O
O	+	DCM, 7 d, 60−75%		OR*	! "
O		DCM, 7 d, 60−75%


169	170		171

R* = isomenthyl; 2-(a-naphthyl)cyclohexyl; 8-phenylmenthyl; 8-(b-naphthyl)menthyl; 8-(3,5-dimethylphenyl)menthyl.

N O

10 kbar, PhMe

+ R2

N Ph

110 C

H O

172

174

173

# #

	O O	RO O	N	O
RO	N		N
RO
	+		H	Ph
	Ph			Ph
		Ph
		Ph

15 kbar

DCM, 17 h Base - NO2

	NO2
RO O O		RO O	O	RO O	O
N	Ph	N	O	N	O
	Ph		Ph	+	NO2
				+
Ph		PhH	NO2	PhH	Ph
		R = Me, Et		Yield = 63-90%

R1	CCl3	12 kbar, DCM		CCl3
	CCl3	12 kbar, DCM		Ts
	+			Ts
	+	70 C, 36 h		N
	N	70 C, 36 h
	Ts		R1		R2
R2	8 examples		Yield = 60-91%
	8 examples		Yield = 60-91%

Py		Py	O
Py		Py			N
					N
N	N	N		N	Py O
N	N	N		N
+ N	Et3N	H N
+ N	N	H
	DCM,	H	14 kbar	Py
	DCM,	Py	14 kbar
Py	r. t., 2 h	Py
Py	r. t., 2 h
5 dienophiles		Yield = 54-91%

O	O
	O
	3 kbar, PhCl	O
	3 kbar, PhCl	O	O
+	N-Ph	O	O
Br	130 C	H	N
Br	O		N
O	O		Ph
O		O
		O
9 dienophiles	Yield = 17-80%
Br		O
Br	O
	O
	3 kbar, PhCl	O
+	3 kbar, PhCl	Br	O
	N-Ph	Br	O
	N-Ph	H
O	130 C	H	N
O	O		N
O	O		Ph
O		O
		O
5 dienophiles	Yield = 44-64%

OMe		O	O	Me	O	Me
		O	O		O	R
		14 kbar, DCM	R	O		R
+		14 kbar, DCM	O	O		O O
+	N	R	N	+	N
	SO2	50 C, 48 h, 86%	SO2	+	SO2
	SO2	O	SO2		SO2
		R = Me	34%		66%
		R = Ph	37%		63%
			LiAlH4			LiAlH4
			THF			THF
		R			R	OMe
		HO	O OMe		O	OMe
		HO			HO

CO2Me

SO2Ph

6% Na(Hg)

12 kbar, MeCN

50 C, >95%

30%

SO2Ph

endo/exo = 1:1

				Ph				Ph
R		R		CN			R	Ph
R		R		CN			R		CN
			+		11 kbar, r.t., 48 h	R			CN
R		R	+		DCM	R1
					DCM
	2		1	N				N
	2		1	S			R2	N

			Tol					S
			Tol	O				S
				(+)			Tol O
				(+)
R = H, Me; R1 = OEt, SPh, Ot-Bu, SMe, OMe, Me;						R2 = H, Me, SMe Yield = 0-99%

	O	O
	SOTol	12.5 kbar, DCM
	+	12.5 kbar, DCM
	+	20 C, 96 h, 55%
		20 C, 96 h, 55%
	O	O
	9 examples	Yield = 19-80%

R1				O
R1				R1
R	O ZnX		(X = Cl, Br), 10-12 kbar O	R1
R	O ZnX	2	(X = Cl, Br), 10-12 kbar O	H
+		2		H
O		DCM, 25 ˚C, 3-5 d		H
				HR
R = n-Pr, CH2Si(OEt)3, CH2CH2OSBT, CH2CH2OBn, CH2OSBT; R1 = Br, CO2Me				Yield 64-80%

H	OMe				O		O
O O		7 kbar, 18 h			H	H
	O					+
		Acetone, 40	C	R		+	H
R O H					CO2Me	MeO2C
R O H					CO2Me	MeO2C
H				H O H O		O HO R
(−)
R = Me, Et, i-Pr, t-Bu, neo-Pn, Ph				Yield = 36-96%		d.e. = 10-86%

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