TETRAHEDRON:

ASYMMETRY
Tetrahedron: Asymmetry 12 (2001) 29312935

Pergamon

Heterogeneous asymmetric DielsAlder reactions using a

copperchiral bis(oxazoline) complex immobilized on mesoporous
silica
Jin Kyoon Park,a Sang-Wook Kim,b Taeghwan Hyeonb,* and B. Moon Kima,*
a

Center for Molecular Catalysis, School of Chemistry & Molecular Engineering, Seoul National University,
Seoul 151 -747, South Korea
b
School of Chemical Engineering, Seoul National University, Seoul 151 -742, South Korea
Received 9 October 2001; accepted 14 November 2001

AbstractA chiral bis(oxazoline)copper complex was immobilized onto mesoporous silica and the resulting heterogeneous
catalyst was employed in asymmetric DielsAlder reactions. Reactions using the catalyst exhibited good enantioselectivity of 78%
enantiomeric excess and endo/exo-selectivity (17:1) better than the corresponding homogeneous reaction. The catalyst could be
easily recovered and reused several times without significant loss of the remarkable reactivity, diastereoselectivity and enantioselectivity. 2002 Published by Elsevier Science Ltd.

The DielsAlder (DA) reaction is one of the most

efficient carboncarbon bond forming reactions affording cycloadducts equipped with a double bond and two
newly formed CC single bonds. Control of the endo/
exo-diastereoselectivity as well as the enantioselectivity
in the DielsAlder reaction has been the focus of
intense investigation and recent years have witnessed
rapid development in the asymmetric DA reaction.1
Among many approaches for asymmetric DA reactions,
methods utilizing chiral catalysts have received much
attention, and a number of Lewis acidic metal complexes employing chiral ligands have been developed.
Recently, Evans2 and Ghosh3 have reported cationic
copper(II)bis(oxazoline) complexes as highly selective
chiral Lewis acids for efficient asymmetric DielsAlder
reactions. However, often relatively large amounts of
the chiral catalysts have been employed due to poor
turnover, leaving room for the development of new,
more practical asymmetric DA methodologies.
Towards the continuous large-scale production of chiral compounds, heterogenization of homogeneous cata-

* Corresponding authors. Tel.: 822-880-6644; fax: 822-872-7505;

e-mail: [email protected]; [email protected]

Part of this manuscript was reported at the National Meeting of the

221st American Chemical Society, San Diego, USA, Org-602, April
4, 2001.

Many
lysts
has
been
extensively
pursued.4
homogeneous asymmetric catalysts were immobilized
onto supports including organic polymers5 and inorganic supports such as silicas and zeolites.6 Recently,
various mesoporous silicas7 with pore sizes ranging
from 2 to 10 nm have been successfully applied as
supports for various chiral catalytic systems.8,9 Herein
we report on the heterogeneous asymmetric DA reaction utilizing novel chiral bis(oxazoline) catalysts immobilized on MCF (meso cellular foam).7
The overall procedure for the synthesis and immobilization of the bis(oxazoline) ligand onto MCF is shown in
Scheme 1. A mixture of diethyl malonimidate and
(1R,2S)-1-amino-2-indanol in dichloroethane was
stirred for 2 days.11 The resulting bis(oxazoline) derivative 1 (indabox) was coupled with p-(bromomethyl)phenyl pivalate or benzyl bromide to produce
2a or 2b, respectively. The pivalate esters of 2a were
removed to provide 3 upon treatment with lithium
aluminum hydride.10 Mesoporous Silica (MCF), composed of uniformly sized spherical cells that are interconnected by uniform windows, was prepared by the
reported method.12 The silica material exhibited surface
area of 970 m2 g1, total pore volume of 1.09 cm3 g1,
cell diameter of 8.61 nm, and window diameter of 3.5
nm. A chloropropyl linker was then grafted onto the
MCF by treating with (CH3CH2O)3SiCH2CH2CH2Cl

0957-4166/01/$ - see front matter 2002 Published by Elsevier Science Ltd.

PII: S 0 9 5 7 - 4 1 6 6 ( 0 1 ) 0 0 5 2 9 - 8

J. K. Park et al. / Tetrahedron: Asymmetry 12 (2001) 29312935

2932

EtO

. 2 HCl

R1

O
NH2 NH

OEt

R1

HO
N

HO

O
3

2a : R1 = OCOC(Me)3
2b : R1 = H

OH
SiO2

O
SiO2

OEt
Si

Cl

e
SiO2

OEt

OEt
Si

OH

OH

OH

OH

OH

SiO2

O
N

OEt

N
HO

OEt
Si

OH

OTMSTMSO

MCF SiO2

OEt

OH

O
O

Scheme 1. Preparation of mesoporous-silica grafted catalysts 5 and 6. Reagents and conditions: (a) (1S,2R)-1-amino-2-indanol,
dichloroethane, 2 days, 70%; (b) p-(bromomethyl)phenyl pivalate or benzyl bromide, LiHMDS, THF, 78C, 3 h, 77 and 82%,
respectively; (c) LiAlH4, THF, 6 h, quant.; (d) chloropropyltriethoxysilane, toluene, reflux, 12 h; (e) 3, toluene, reflux, 12 h; (f)
HMDS, reflux, 12 h.

in refluxing toluene. Reaction of 3 with chloropropylderivatized MCF 4 yielded the indabox-grafted silica 5.
In order to protect the remaining free SiOH groups on
the walls of mesoporous silica, 5 was treated in refluxing hexamethyldisiloxane (HMDS) for 12 h and the
resulting 6 was vacuum-dried (<0.01 torr) at 130C for
12 h. The resulting bis(oxazoline)-ligand grafted, TMScapped MCF 6 exhibited surface area of 542 m2 g1,
total pore volume of 0.65 cm3 g1, cell diameter of 7.48
nm, and window diameter of 3.6 nm. The grafted
amount of chiral ligand was 0.240.17 mmol g1 of
silica support.

2-oxazolidinone 7, 3-(2(E)-butenoyl)-2-oxazolidinone 8,
or 3-((2E)-pentenoyl)-2-oxazolidinone 9 as the
dienophile in CH2Cl2 for 24 h using 10 mol% of the
silica-grafted chiral ligand, which was premixed for 3 h
with varying amounts of Cu(OTf)2 as shown in Scheme
2. The results are summarized in Tables 1 and 2.
First, a control reaction between cyclopentadiene and
the acryloyl derivative 7 employing the parent homogeneous catalyst 2b (11 mol%) and Cu(OTf)2 (10 mol%)
was carried out at 78C to provide a 96% yield of a
mixture of endo- and exo-adducts in a 9:1 ratio, with
the endo-diastereomer having 88% e.e. by chiral HPLC
analysis (entry 1). When the DA reaction of the same
substrates employing heterogenized chiral ligand 6 (10

The DA reactions were carried out using cyclopentadiene or cyclohexadiene as the diene and 3-(2-propenoyl)-

O
O

SiO2

OEt
Si
O

OEt

O
O

Cu(OTf)2

OH

OEt

OEt
O

OH

CH2Cl2, 3h

OTMS
TMSO

SiO2

Si

OTMS
TMSO

A
n
O

n
+
n = 1, 2

O
N

10 mol % A

7, R = H
8, R = Me
9, R= Et

Scheme 2. DielsAlder reaction catalyzed by silica-indabox A.

CH2Cl2, ToC

N
O

O
O

10, R = H (n = 1),
11, R = H (n = 2)
12, R = Me (n = 1)
13, R = Et (n = 1)

Cu2+
2OTf-

J. K. Park et al. / Tetrahedron: Asymmetry 12 (2001) 29312935

2933

Table 1. Asymmetric DielsAlder reaction between cyclopentadiene and 7 using 10 mol% of 6

Entry

Amounts of Cu(OTf)2 (mol%)

1a
2b
3b
4c
5b
6b
7b
8
9
10d

10
6
6
10
10
10
30

10
10

T (C)
78
0
0
0
50
70
70
70
78
78

Yield (%)e

endo/exo f

96
99
99
99
99
97
97
22
99
99

9:1
10:1
8:1
9:1
9:1
12:1
11:1
10:1
13:1
17:1

endo (% e.e.)f
88
15
39
11
50
65
65

75
78

Reaction was carried out in solution phase.

Washing conditions are detailed in the text.
c
Washed with acetone twice.
d
Reaction using catalyst 5.
e
Yield was determined through 1H NMR (300 MHz) analysis based on remaining starting material. 1H NMR yields were almost identical to the
isolated yields.
f
Enantio- and endo/exo-selectivities were determined through HPLC analysis using Chiralcel OD column (1 mL/min, 10% iPrOH in hexane) and
1
H NMR (300 MHz).
b

Table 2. Asymmetric DielsAlder reaction between cyclopentadiene (cPt) or cyclohexadiene (cHx) and various dienephiles
79 at 0C in the presence of 10 mol% 6 and 10 mol% Cu(OTf)2
Entry

Diene

Dienophile

Yield (%)d

endo/exo e

endo (% e.e.)e

1a
2
3a
4
5a,b
6c

cPt
cPt
cPt
cPt
cHx
cHx

8
8
9
9
7
7

95
99
95
99
95
53

3:1
4:1 (4:1)f
3:1
4:1 (4:1)f
\99:1
\99:1

85
72 (72)f
82
65 (60)f
61
53

Reactions carried out in solution phase.

Reaction was run for 3 days.
c
Reaction was run for 7 days.
d
Yield was determined through 1H NMR (300 MHz) analysis based on remaining starting material.
e
HPLC Conditions for determination of isomeric ratios (12: Chiralcel OD-H column, 1 mL/min, 2% reagent ethanol in hexanes; 13: 0.9% iPrOH
in hexanes through Chiralcel AD column; 11: after conversion to the corresponding iodolactone, temp. 160C 1.5 mL/min through Cyclodex-b
(J & W)).
f
Numbers in parentheses are the results obtained from repetition experiments using the recycled chiral ligand.
b

mol%) and 6 mol% of Cu(OTf)2 was carried out at 0C,

the cycloadducts were obtained in almost quantitative
yield (99%) with endo-selectivity of 10/1, however the
endo-isomer exhibited only 15% e.e. (entry 2). We
reasoned that even with 0.6 equiv. of Cu(OTf)2 to the
chiral ligand, some uncomplexed copper reagent might
still remain in the mixture, lowering the enantioselectivity of the reaction. In order to remove free copper
species from the reaction mixture, the Cu-complexed
silica was washed with CH2Cl2 before the reaction and
a noticeable improvement in the enantioselectivity (39%
e.e.) was observed under otherwise identical reaction
conditions (entry 3). However, when the silica was
washed with acetone instead of dichloromethane to
ensure complete removal of free Cu(OTf)2, the enantioselectivity of the reaction dropped precipitously (11%
e.e.), though the yield of the reaction and the endo/exoselectivity remained unchanged (entry 4).13 To examine
the temperature effect, the reaction was carried out at
50C using the catalyst prepared from 10 mol% of

Cu(OTf)2 and silica followed by washing with

dichloromethane. The enantioselectivity of the reaction
increased, giving 50% e.e. with a similar level of endoselectivity (entry 5). The enantioselectivity and endoselectivity were further improved (65% e.e. and 12/1,
respectively) when the temperature was lowered to
70C (entry 6). In an attempt to ensure complete
removal of uncomplexed copper species from the silica
surface, the silica 6 was treated with 30 mol% of
Cu(OTf)2 and washed with dichloromethane (three
times), stirred with 10 equiv. of 3-acryloyloxazolidin-2one in dichloromethane for 10 h at room temperature
and finally washed with dichloromethane (three times).
Even after this extensive washing, the DA reaction
proceeded with the same enantioselectivity (65% e.e.)
and in almost quantitative yield (99%) (entry 7). This
indicates that the free copper species might not be
responsible for the reduction in the enantioselectivity at
the lower temperature. Indeed, 20 and 2% yields of the
endo- and exo-products, respectively, were obtained

J. K. Park et al. / Tetrahedron: Asymmetry 12 (2001) 29312935

2934

Table 3. Recycling DA reaction between cyclopentadiene and 7 at 78C

Catalyst 5
Catalyst 6
a
b

14

Method

1st (endo/exo)

2nd (endo/exo)

3rd (endo/exo)

4th (endo/exo)

5th (endo/exo)

A
B
A

75 (15:1)
78 (17:1)
67 (13:1)

71 (13:1)
72 (15:1)a
75 (13:1)

69 (12:1)
73 (16:1)
48 (14:1)

63 (13:1)
70 (14:1)
56 (13:1)b

72 (15:1)b
52 (13:1)

The reaction was run at 73C.

Additional Cu(OTf)2 (1 equiv.) was added at this run.

when a DA reaction was carried out using the ligandgrafted silica 6 without copper reagent at 70C for 24 h
(entry 8). This result clearly indicates that the TMScapped silica 6 exerts some catalytic activity in the
DielsAlder reaction even at 70C. When the temperature was lowered to 78C, the highest enantioselectivity was observed (75% e.e., entry 9). It is of particular
note that increased endo/exo-selectivity (13/1) compared to that obtained in the homogenous reaction was
observed using the immobilized catalyst. In the reaction
using catalyst 5, which is not protected with the TMS
group (entry 10), the enantio- and endo/exo-selectivity
were higher than those obtained with catalyst 6 (78%
e.e. and 17/1, respectively). All of the reactions examined in Table 1 employing the immobilized catalyst 5
and 6 afforded almost quantitative yields (>97%) indicating excellent catalyst reactivity.
To examine the scope of the reaction employing the
catalyst 6, we carried out DA reactions using various
dienes and dienophiles, the results are summarized in
Table 2. When a reaction employing cyclopentadiene
and the dienophile 8 in the presence of the homogenous
catalyst 2b was carried out at 0C, the DA cycloadducts
were obtained with 3/1 endo-selectivity and the endoisomer 12 was obtained with 85% e.e. (entry 1). When
the same reactions were carried out using 10 mol% each
of heterogenized ligand 6 and Cu(OTf)2, a 4:1 mixture
of endo- and exo-products was obtained with 72% e.e.
for 12 (entry 2). A homogeneous DA reaction between
cyclopentadiene and dienophile 9 employing 2b gave
the endo-isomer 13 with 82% e.e. and endo-selectivity of
3:1 (entry 3). In heterogeneous reactions employing 6,
the e.e. of 13 was 65% and endo-selectivity was 4:1
(entry 4). In a preliminary attempt to test the recyclability of the catalyst from the reactions of entries 2 and 4,
almost the same diastereo- and enantioselectivities were
observed (numbers in parentheses in entries 2 and 4).
When a homogenous reaction employing cyclohexadiene and the dienophile 7 was carried out at 0C, the
DA cycloadducts were obtained with endo-selectivity of
>99/1 and the endo isomer 11 had 61% e.e. (entry 5).
With heterogenized ligand 6, the endo-product (with
53% e.e.) and endo/exo-selectivity of >99:1 were
observed (entry 6). Both reactions of cyclohexadiene
proceeded very slowly. The fact that there are 817%
differences in the e.e. between homogenous and heterogeneous reactions indicates that some reactions are
catalyzed by sources other than the immobilized catalyst prepared from 6.

Encouraged by the results from the preliminary recycling experiments (entries 2 and 4, Table 2), we further
examined the recycling capability of the catalysts 5 and
6.14 Reactions were carried out with the catalyst prepared from adding 30 mol% of Cu(OTf)2 to 10 mol% of
5 or 6 followed by washing extensively with
dichloromethane. According to different ways of washing the catalyst, two different protocols have been
employed. In method A, after mixing the silica ligand
and Cu(OTf)2 in dichloromethane, the mixture was
stirred for 3 h, washed with dichloromethane and dried
before use. In method B, after stirring the silica ligand
with Cu(OTf)2, the mixture was diluted with a large
amount of dichloromethane and stirred for another 0.5
h, filtered and dried before use. After 24 h reaction, the
mixture was filtered and the solid residue was washed
with hexane twice. The recycling experiments were carried out using new batches of diene and dienophile and
the results are summarized in Table 3. When TMScapped ligand 6 was utilized using method A, almost
consistent endo/exo-selectivity was observed and the
e.e. of the endo-product peaked at the second run (75%)
and gradually decreased. When the ligand 5 was examined under the same method (A), the enantioselectivies
were similar initially and stayed above 60% e.e. up to
the 4th recycle. When method B was employed for
catalyst 5, much more consistent enantioselectivities
(over 70% e.e.s) were observed. Further study will be
required to clarify the reason why catalyst 5 gives better
results than catalyst 6.
To address the possible cause of the observed gradual
decrease in enantioselectivity upon repeated use of the
ligand, we examined the copper quantity after repetition experiment using 5 through EPMA (electron probe
microanalyser) analysis and the results are listed in
Table 4. From the data, it was obvious that the copper
content decreased considerably after each run and this
might have caused the slight reduction of enantioselectivity. In Table 3, after additional Cu(OTf)2 was added,
the reaction enantioselectivity rebounded a little.

Table 4. Leaching experiment with method B through

EPMA

Si:Cu

1st

2nd

3rd

89.6:10.4

91.9:8.1

94.2:5.8

J. K. Park et al. / Tetrahedron: Asymmetry 12 (2001) 29312935

Conclusions
In summary, we have prepared a new heterogeneous
catalyst system containing a chiral bis(oxazoline) ligand
immobilized onto MCF. The immobilized catalyst
exhibited good enantioselectivity of up to 78% e.e. and
high endo/exo-selectivity of 17:1 in the reaction
between cyclopentadiene and the dienophile 7. When
cyclohexadiene and other dienophiles were examined
with the heterogeneous catalyst system, the enantioselectivities were found to be 817% lower than the
corresponding homogeneous reaction enantioselectivies.
The catalyst was easily recovered and reused several
times without losing its high reactivity and
enantioselectivity.
Acknowledgements
We would like to thank the Brain Korea 21 Program
supported by the Ministry of Education for the financial support. B.M.K. acknowledges the support from
the KOSEF through the Center for Molecular Catalysis
at Seoul National University.

8.

9.

10.

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Physical data of 3: 1H NMR 3.072.91 (m, 6H), 3.403.31
(m, 4H), 5.33 (t, J=7.1 Hz, 2H), 5.48 (d, J=8.7 Hz, 2H),
6.31 (d, J=8.3 Hz, 4H), 6.62 (d, J=8.3 Hz, 4H), 7.397.28
(m, 8H); 13C NMR 38.6, 40.0, 50.0, 80.0, 85.1, 115.9, 126.3,
126.6, 127.1, 128.6, 129.8, 132.3, 141.3, 142.4, 157.7, 169.7;
[h]26
D =133 (c 1, MeOH); LCMS m/z 543.5; HRMS (FAB+)
m/z 543.2301 (calcd for C35H30N2O4 +H+ 543.2284).
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Presumably binding of acetone to copper might have
altered the reaction transition state geometry.
Typical experimental procedures:
Method A: Indabox-immobilized silica (40 mg, 0.23 mmol
g1) was mixed with Cu(OTf)2 (23 equiv. to the ligand)
in CH2Cl2 (1 mL). The mixture was stirred for 3 h and the
solid residue was washed with CH2Cl2 (5 mL) and dried
under reduced pressure. Then the silica-copper complex
was charged with CH2Cl2 (0.7 mL) and a dienophile. At
the specified temperature cyclopentadiene (10 equiv.) was
added. After the dienophile disappeared completely
according to TLC analysis, the silica copper complex was
washed with CH2Cl2 (5 mL) and dried under reduced
pressure.
Method B: Indabox-immobilized silica (40 mg, 0.23 mmol/
g) was mixed with Cu(OTf)2 (23 equiv. to the ligand) in
CH2Cl2 (1 mL). The mixture was stirred for 3 h and then
charged with additional CH2Cl2 (10 mL) and stirred for 30
min. The solid residue was filtered and dried under reduced
pressure. Then the silica copper complex was charged with
CH2Cl2 (0.7 mL) and a dienophile. At the specified
temperature cyclopentadiene (10 equiv.) was added. After
the dienophile disappeared according to TLC, the silica
copper complex was washed with hexane (10 mL) and dried
under reduced pressure.