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Казанский национальный исследовательский технологический университет

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The Diels-Alder Reaction

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<<< < Предыдущая 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 2627 / 3527 28 29 30 31 32 33 34 35 > Следующая >>>

	CO2Me		MeO2C	OCbz
			H	OCbz
		15 kbar, PhMe, 50	C	OCbz
		24 h, 70-80%		OCbz
CbzO	OCbz	24 h, 70-80%
CbzO	OCbz		H	OCbz
	OCbz		H	OCbz
	OCbz
	3 examples

TolOS SOTol			13 kbar, DCM
	+		13 kbar, DCM

			r.t., 24 h, 72%
EtO2C CO2Et			r.t., 24 h, 72%
EtO2C CO2Et
(S,S) (+)
4 examples		Yield = 10-82%

SOTol	+
SOTol	+
CO2Et

CO2Et 87%

CO2Et

SOTol

13%

NPht			NPht	NPht
	+	0.25-3.0 kbar, DCM	+
	+		+	O
	O		O	O
X3C O		X3C O		X3C O
		O
X = F, Cl	Pht =	5 examples	Yield = 48-95%
		O

					H
	CN	OMe	1. 15 kbar, PhMe		O
	CN	OMe	1. 15 kbar, PhMe
PhO2S N	+		r.t., 4 d, 66%	PhO2S N	CN
PhO2S N	+		2. CSA	PhO2S N	CN
			2. CSA		O
	O		OSMT		O
	O		OSMT

66 %

SO2R	+		10 kbar, PhMe	CF3	SO2R
SO2R	+		40 C, 14 h	+
F3C			40 C, 14 h	SO2R	CF3
				SO2R	CF3
Ph	O		O Ph
R =	O		5 dienes	Yield = 40-75%
	O	N	O
		N

O
R	13 kbar, DCM
	13 kbar, DCM
	+
R1	2 d, 86%
R1
MeO OMe

O H	OH
R	R

R1	H	R1
MeO	OMe	OMe

R = Et, R1 = H ; R = H, R1 = Me Yield = 31-96%

# M

O	3 kbar, C6H4Cl2	O	TFA	O
				C60
+ C60	24 h	C60
O		O		HO

33% overall yield

	O	Ph
	O	N			O	NHCbz
	O	O			O	NHCbz
	O	O		O		CO2Me
				O
		O
		O	OSMT
	12.5 kbar, DCM		OSMT	14 kbar, DCM
	12.5 kbar, DCM			14 kbar, DCM
	r.t., 6 h, 91%			60 C, 120 h, 70%
TMSO HO	O		TMSO H NHCbz		TMSO H NHCbz		TMSONHCbz
	Ph		CO2Me			CO2Me		CO2Me
	N		H			H	+	H
	H		H		+	H	+	H
	O		O			O		O
O			O			O		O
			major					minor

		H O			H O
O OR1			R1O			O OR1
R2			R1O			R2

	Ln cat:, 15 kbar,				Ln cat:, 15 kbar,
R3	Ln cat:, 15 kbar,		R2		Ln cat:, 15 kbar,	R3
R3	r.t., 16-72 h, 65-85%			R3 50 C, 72 h, 36-37%		R3
	r.t., 16-72 h, 65-85%			R3 50 C, 72 h, 36-37%
R1 = i-Pr, R2 = Me, R3 = H					R1 = Et, R2 = Me, R3 = Me

OMe	H
H	H
H	H
OMe
	OMe
PhMe,
125 C, 8 kbar,
4 d, 60 %
	OMe
	OMe
H

H MeO H

OMe H

MeO

			Ph	Ph
	OMe	Ph	O	O	OMe
				TiCl2
O	O	Me	O	O	O
		Me	O		O
			Ph	Ph	H
			Ph	Ph	H
	N	1-5 kbar, DCM, r.t., 81-95 %			N
	N	1-5 kbar, DCM, r.t., 81-95 %			O
					O
O	N	O			O N O
O	N	O

ee = 4.5 (1 bar) ee = 20.4 (5 kbar)

O				H H	O
O		10 kbar, DCM			O
+	O	10 kbar, DCM		O
					NH
		50	C, 24 h, 73 %
NH		50	C, 24 h, 73 %
MeO2C				MeO2C H
				MeO2C H
	4 dienes			Yield: 70-88 %

					O	H
					O	H
					O
					H
Ph	O	O		O
Ph
N
N	H	N Ph		O	H
O	H	N Ph		O	H
O					CO2Me
H		O		O	CO2Me
H		O		O	+
	10 kbar, DCM				+
	10 kbar, DCM			10 kbar, DCM		H	O
	80	C, 48 h, 68%	H	85 C, 70 h, 27%		H	O
	80	C, 48 h, 68%	H	85 C, 70 h, 27%
H			CO2Me				O
CO2Me						H
						H	O

CO2Me

NO2 O−			O2N
NO2 O−	Ph	8 kbar, DCM
S +	+	8 kbar, DCM	S +
(S)	+	r.t., 5 d, 80%
(S)		r.t., 5 d, 80%
			−O

3 dienophiles, 5 dienes, Yield = 39-81 %

	O
	E
		O			E
		H			E
		H
	ZnBr2, 12 kbar,	E		+
	ZnBr2, 12 kbar,	E			O
	DCM, 23 h, 65%				O
					OH
		major
	E = CO2Me
				O	O O		O
		O		HO	O O		O
ZnBr2, 12 kbar,		O	O
ZnBr2, 12 kbar,		O	O
	DCM, 23 h	H	+	E	+	E
		H		E		E

	O	E
O	O

major

# M

H			MeO		H
MeO	CO2Me				CO2Me
		1. 10 kbar, DCM
N	OSMT				O
	O +	40-50%	MeO		N
MeO		O 2. SiO2
					O
MeO2C	O	Me		O	CO2Me
					OMe

				NHCbz		NHCbz
		NHCbz
+	H		Eu(fod)3, 15 kbar	H	+	H

			Ether, 50 C, 24 h
			Ether, 50 C, 24 h	O	OBOM	O OBOM
OMe	O OBOM			OMe		OMe
				OMe		OMe

4 dienophiles

		H
	10 kbar, PhMe	H
+	10 kbar, PhMe		H
+	80 C, 96 h
N O	80 C, 96 h	N
N O			O
O R			O
O R		O
		R
R = H, Me	Yield = 11-19%

			H		H
			O		O
	O		H		H
			H		H
7.5 kbar, DCM					+
7.5 kbar, DCM			H		H
50 C, 2 d, 56%			H		H
			O		O
			H		H
7.5 kbar, DCM				H	H
55	C, 3 d, 85%	O	O		O	O
		O	O		O	O
O	O			H	H

10 kbar, PhMe

N Ph

110 C, 3 d, 13-96%

N O

R = R1 = R2 = R3 = H, Ph

endo/exo = 0.5−9.5


M
	M

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