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Казанский национальный исследовательский технологический университет

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The Diels-Alder Reaction

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		M
O		OMe
O	DCM, −45 C	O
	DCM, −45 C	O
O	Me3SiOTf-Me3SiOMe	O	10 h	O O
	O		89%;	O
				O
98		99		endo/exo = >110:1 ! "

PhH, LiBF2

r.t., 72 h, 100%

O	R1		O Br	R1
O	R2		O Br		R2
Br	R2	MeCN, SnCl4, r.t.			R2
Br	+	MeCN, SnCl4, r.t.
	+	17−62 h, 75−91%	n( )
n( )	R	17−62 h, 75−91%	n( )		R3
n( )	3		H		R3
			H
n = 1, 2					PhH, DBU,
n = 1, 2					PhH, DBU,
R1, R2, R3 = H, Me					r.t., 0.6−1.5 h,
R1, R2, R3 = H, Me					84−96%
four dienes:	75−91%				84−96%
		O	R1		O	R1
			R2	+		R2
				+
		n( )	R3		n( )	R3
			R3			R3
			H

Ph	S		X* DCM, Cat., −78 to −20 C Ph			S	Ph	S
			X* DCM, Cat., −78 to −20 C Ph			S	Ph	S
N		+				+
N		+		3 h, 58−95%, de = 50−70% N		+	N
		O		3 h, 58−95%, de = 50−70% N		COX*	N	COX*
	N	O				COX*		COX*
Me	N					N		N
Me	Me				Me	N	Me	N
					Me	Me	Me	Me
						major		minor
X* =	O	CO2Et	Cat = TiCl4, TiCl2(O-iPr)2, EtAlCl2, Et2AlCl, MgBr2; Yield: 58−90%
X* =
		O
X* =	N	O	Cat = MgBr2; Yield: 95%, de = 100%

# # M #

XNi(COD)2PPh3

ClCH2CH2Cl				O
				O
X
Dienophiles: X = CHO, COMe, COt-Bu, CN, SOPh, SO2Ph,	( )n ,		,	N Ph
O		O	O
		O		O
				O

	O		O
MeO2C			SPh
MeO2C	SPh	PhMe, EtAlCl2, r.t. H	MeO2C
	N	PhMe, EtAlCl2, r.t. H	N
	+	60−70%	O
		OSMT	H

no reaction without catalyst.

HO							R3
	H	R3		DCM, Cat*				R2
N	+			DCM, Cat*

				−15 to 45	C, 52−90%, ee: 61−91%
	H	R2		−15 to 45	C, 52−90%, ee: 61−91%			R1
R1	H	R2					N	R1
R1	H						OH H
							OH H
R1, = Ph, α-Napht, C6H11
alkenes:		OEt ,	OBu ,		,	,

additives: DPP, DTBP, DTBMP

R1	R	Cat.		R1 +	H
+		5 − 78%	R	R1 +	H
H	CHO	5 − 78%	R		CHO
H	CHO		H		R1
			H		R1
			CHO		R

R, R1= H, Me

R	H	(S)-BINOL/Ti(Oi-Pr)4
+		(S)-BINOL/Ti(Oi-Pr)4	CHO
+	O	DCM, −20 to −78 C, 0.1−24 h	CHO
		DCM, −20 to −78 C, 0.1−24 h	R
		70−94%, ee: 50−94%


R = Me, Br			endo/ exo = 17:1

O	O
O
	N O +						DCM, Cat*		R1+
R1	N O +						−78 C		R1+	R1
R1							−78 C			R1
							ee: 64−98%			O X
R1 = H, Me								O	X
	Me		Me				2	R = t-Bu, M = Cu
	O			O				R = t-Bu, M = Cu
Cat*	O			O				R = Ph, M = Zn
Cat*								R = Ph, M = Zn
	N	M	N				2 SbF6
	R	M					2 SbF6
	R				R
	O							2 M = Cu, Zn
Cat*	O	N				O		The Cu-based catalysts were found to be superior
Cat*								The Cu-based catalysts were found to be superior
	N	M	N					2 SbF6
								2 SbF6
	Ph					Ph

O		DCM, Cat., 15−240 h	R2O O
SO2Ph	+ R1CH=CHOR2	DCM, Cat., 15−240 h	SO2Ph
SO2Ph	+ R1CH=CHOR2
R		−50-r.t., 24−97%	R1

R endo

R = H, Me, i-Pr, Ph; R1 = H, Me, Ph; R2 = Et, i-Bu, Ph

Cat = ZnI2, Eu(fod)3, TiCl2(Oi-Pr)2

O	O
Me	Br
H	H

The observed enantioselectivity was zero or very low.

ROC X

X	PhMe, MeAlCl , −78 C
	2

	+
		1 h, 54−97%
	COR

X = H, Me, OAc; R = H, NHBz

four dienes; six dienophiles; catalyst: MeAlCl2, SnCl4

Ph	O	O				O
		O		Ph	O	O
			DCM, 0 C, 2 h	Ph	O
+		N O	DCM, 0 C, 2 h
+	R	N O	Me2AlCl or TiCl4			N O
Ph S	R		Me2AlCl or TiCl4
Ph S			9−99%
			9−99%	Ph S	R
		Ph		Ph S	R
		Ph				Ph
	R = H, Me			endo:exo = 99:1 to 61:39

M ! "

	R1				R1
	R1
				H
R3	R2 +		20 mol% InCl3, r.t.		R2
	R2 +		0.5−0.7 h, 58−95%		NH
	N		0.5−0.7 h, 58−95%		NH
	N			H
				H
	H
R1 = H, Cl, NO2, OMe; R2 = H, Me, Et, NO2, COOH
R3 = H, Me, Cl					R3
	R				R	R
	R
	O			O		H
				H		H
	+	MeCN, InCl3, r.t.			+
	+		24 h, 60−70%		+	NH
	Ph N		24 h, 60−70%		NH	NH
	Ph N			H		H
				H	O	H
	H			Ph	O	Ph
	H
	R = H, Cl, NO2, OMe


R1 COR		DCM, MAO, 0.5−42 h
	+	DCM, MAO, 0.5−42 h			+

		0 C to −78 C, 85−99%				COR
		0 C to −78 C, 85−99%			R1	COR
				COR		R1
	R = H, Me, OMe; R1 = H, Me		Me
	Methylalumoxane = MAO =	Al
			O n

% ! " &

O	hexane, 30 mol% Sc(OPf)3		O
	hexane, 30 mol% Sc(OPf)3		O
	+
H R	+	r.t., 24−96 h, 41−98%	R
H R		r.t., 24−96 h, 41−98%

R = Ph, p-XC6H4 (X = NO2, Cl, Me, OMe, Ph, NO2),

-Naphthyl, PhCH2CH2, C6H11, C6H13

PhMe, 0 C, AlCl3

+ 3.5 h, 60%

six dienophiles: 35−80%

	H O
+			DCM, Cat*, 14−17 h		R
+		−94 to	−78 C, 37−83%, ee: 80−87%
		−94 to	−78 C, 37−83%, ee: 80−87%
	R				CHO
	R
R = TMS, TES, Me2PhSi, Bu3Sn
		Br
		B	O
Cat* =		N	O	B[C6H3-3,5(CF3)2]4
Cat* =				B[C6H3-3,5(CF3)2]4

+	PhMe, −78 to −20 C			+
+			H	+	CHO
O 8.5 h, Cat (A, B, C)			H		CHO
			CHO		H
		Cat.	Endo/Exo		Yield (%)

		A	76	24	77
		B	81	19	50
		C	−	−	traces

Li	Li	Li	Li	Li
O	O	O	O	O
t-Bu		t-Bu t-Bu		t-Bu t-Bu
t-Bu	t-Bu	t-Bu	t-Bu	t-Bu
	A		B	C

		R1	CHCl3, BiCl3,		R1		HO	R
	O	R2		R2
			20 to 60 C		O	+	R2	CO2Et
R	CO2Et	+	0.3−24 h, 47−96%		R

					CO2Et		R1

R = H, CO2Et; R1, R2 = H, Me

major

minor

! "

Petrol Ether or DCM, 60 or −78 C

MeO 1−60 h, 10−99%, Cat. O RO

	Ph	Ph	Ph
	H	H	H
	+		+
MeO	MeO	O	MeO
	O	O	O
	OR	OR	OR
	O	O	O
	endo	exo	abnormal

R = Me, SiMe2t-Bu, SiPh2t-Bu, SiMe3; Cat = Eu(fod)3, SnCl4, TiCl4

In the presence of Eu(fod)3 the endo-cycloadduct is the predominant reaction product; in the presence of SnCl4 the abnormal product is predominant

	O				O	S O		O	S O
S	O	DCM, SnCl4, −78 C			X P	S O		X P	S O
S		DCM, SnCl4, −78 C			X P	N	+	X P	N
N O		+	5 min, 41−90%		Y		+	Y
					Y			Y

X	P					exo			endo
X	Y					exo			endo
	Y
X, Y = (EtO)2; (MeO)2; Ph2,			O	O	,	O
X, Y = (EtO)2; (MeO)2; Ph2,			O ,	N	,	N
				Pr		t-Bu

M
M
	O				O
+	O	R	AlMe3/AlCl3	R	O
+	O	R	−20 C - r.t., 50−91%	R	O
			−20 C - r.t., 50−91%

n = 1, 2

R = Me, Ph; endo/exo from 2:1 to 7:1

HO				OH
HO	OSMT
	OSMT		PhMe, Cat.*	R1
	+		PhMe, Cat.*	R1
N	+	OMe	− 45 C, 47−98%, ee = 64−93%	N
N		OMe	− 45 C, 47−98%, ee = 64−93%
R	R1		R	O
R	H
R = a-Naphthyl, o -MeC6H4, Ph, Me(OMe)2C6H3, 2-Thienyl, Cy;
R1 = H, Me; L = NMI, DMI
	Br		Br
		L
	Cat* =	O	O
	Cat* =	Zr	L = Ligand
		Zr
		O	O
		L
	Br		Br

H	DCM, Cat*, −20	C, 20 h
+			CHO
	68−83%, ee	97%
O

2,6-di-t-butylpyridine	exo/endo = 49

BF4

Cat* = (C6F5)2P P(C6F5)2 L = acrolein, benzaldheyde

O L O

Ph Ph

three aldehydes: three dienes



H	PhMe, Cat.
+	PhMe, Cat.		H
+	−78 C or	r.t., 99%
O
O			COH
			COH
			endo/exo = 3.5
four dienophiles, three dienes:
	n		n
		Ph	Ph
Ph	Ph		Ph	Ph
Cat =	O		O	O Ph
	PhOAl		Al	O Ph
	O	Ph	Ph O
n	Ph		Ph	n
n				n

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