Novel Sc(OTf)3/3-HQD catalyst for Morita-Baylis-Hillman reaction

Article abstract of DOI:10.1080/00397910802474958

A novel and efficient catalytic system of the Morita-Baylis-Hillman (MBH) reaction between aromatic aldehyde and activated alkenes has been developed. The novel system of a combination of Sc(OTf)3 and 3-hydroxyquinuclidine (3-HQD) showed a high catalytic

Full text of DOI:10.1080/00397910802474958

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Novel Sc(OTf)3/3-HQD Catalyst
for Morita–Baylis–Hillman
Reaction
Yongjia Shang a , Dongmei Wang a & Jing Wu a
a College of Chemistry and Materials Science, Anhui
Key Laboratory of Functional Molecular Solids, Anhui
Normal University , Wuhu, P. R. China
Published online: 25 Feb 2009.
To cite this article: Yongjia Shang , Dongmei Wang & Jing Wu (2009) Novel Sc(OTf)3/3-
HQD Catalyst for Morita–Baylis–Hillman Reaction, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:6,
1035-1045, DOI: 10.1080/00397910802474958
To link to this article: http://dx.doi.org/10.1080/00397910802474958
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Synthetic Communications1, 39: 1035–1045, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802474958
Novel Sc(OTf)3/3-HQD Catalyst for
Morita–Baylis–Hillman Reaction
Yongjia Shang, Dongmei Wang, and Jing Wu
College of Chemistry and Materials Science, Anhui Key Laboratory of
Functional Molecular Solids, Anhui Normal University, Wuhu, P. R. China
Abstract: A novel and efficient catalytic system of the Morita–Baylis–Hillman
(MBH) reaction between aromatic aldehyde and activated alkenes has been devel-
oped. The novel system of a combination of Sc(OTf)3 and 3-hydroxyquinuclidine
(3-HQD) showed a high catalytic activity for the MBH reaction.
Keywords: 3-Hydroxyquinuclidine, Morita–Baylis–Hillman reaction, Sc(OTf)3
INTRODUCTION
The Morita–Baylis–Hillman (MBH) reaction,[1–6] an important reaction,
has been added to the list of the useful carbon–carbon bond-forming
reactions. Since the MBH reaction possesses the two most important
requirements, atom economy and generation of functional groups, it qua-
lifies to be in the list of efficient synthetic reactions.[7] However, the major
drawback of the MBH reaction is its slow reaction rate (e.g., the reaction
of tert-butyl acrylate with benzaldehyde using 10 mol% DABCO catalyst
takes 28 days to complete).[8] So, it was very significant to develop a novel
efficient synthesis for the reaction. A number of physical and chemical
methods have been developed to accelerate the notoriously slow MBH
reaction.[9] For example, the Aggarwal group has found that the use of
Sc(OTf)3 (5 mol%) in the MBH reaction with 1,4-dimethylaminopyridine
Received March 26, 2008.
Address correspondence to Yongjia Shang, College of Chemistry and
Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui
Normal University, Wuhu 241000, China. E-mail: shyj@mail.ahnu.edu.cn
1035

1036
Y. Shang, D. Wang, and J. Wu
(DABCO) (100 mol%) as the catalyst resulted in an acceleration of the
reaction [Krel (DABCO) ¼ 3.3], but the yield can increase up to only
11.6% after 24 h when the reaction was conducted using tert-butyl acry-
late and benzaldehyde.[10] Then, after a few years, they found that 3-
HQD with GnCl can also caused an increase in the rate of the reaction
in water [Krel (DABCO) ¼ 9.5]. In contrast to not using Lewis acid, no
additional rate acceleration was observed with Sc(OTf)3 in water.[11]
Herein, we report a novel and efficient condition for the MBH reaction
using Sc(OTf)3 and 3-HQD as cocatalysts and dimethylformamide
(DMF) as the solvent.
RESULTS AND DISCUSSION
To establish the reaction conditions, we first examined the reaction of
p-nitrobenzaldehyde and methyl acrylate in CH3CN and investigated
the effect of different amine catalysts on reaction rate as shown in
Scheme 1, and the results are summarized in Table 1. We found that
no reaction occurred when using pyridine as a Lewis base (Table 1,
entry 3). As expected, no product was observed after stirring for 24 h
at 20 ꢀC when Sc(OTf)3 alone was employed as the catalyst. DMAP
has been compared with imidazole and found to be superior in the reac-
tion between p-nitrobenzaldehyde and methyl acrylate in CH3CN. We
found that DMAP was indeed better than imidazole, but with reactions
conducted neat, 3-HQD gave the highest yield and fastest rate. Therefore,
we selected 3-HQD as the base in MBH reaction for further investigation.
It is well-known that the MBH reaction is affected by solvents. Auge
has shown that the MBH reaction between acrylonitrile and various
aldehydes can be accelerated in water.[12] However, they had chosen to
study reactions involving acrylonitrile, as this is already a relatively
fast-reacting substrate in the MBH reaction. Besides this, we also focused
on slower reacting substrates: acrylates. We found that water did not
work well in these reactions, but to our delight, the use of DMF as a
solvent allowed for a dramatic increase in the yield of the MBH reaction
(Table 2, entries 4–10). Also, we found that raising the temperature
accelerated the reaction and led to increase in yield. The optimal reaction
Scheme 1. Morita–Baylis–Hillman reaction.

Sc(OTf)3/3-HQD Catalyst for MBH Reaction
1037
Table 1. Effect of base on the MBH reactiona
Entry
Lewis base
Time (h)
Yield (%)b
1
2
3
4
5
Imidazole
Et3N
Pyridine
3-HQD
DMAP
24
24
24
3
30
23
—
59
44
24
aReaction conditions: 3.0 mmol of methyl acrylate, 1.0 mmol of p-nitrobenz-
aldehyde, 100 mmol% of Lewis base using CH3CN as solvent.
bIsolated yield based on p-nitrobenzaldehyde.
temperature for the reaction was 40 ꢀC (Table 2, entries 11 and 12);
higher reaction temperature did not significantly improve the result.
Based on these results, the reaction was best conducted in DMF
at 40 ꢀC with 5 mol% of catalyst in a 1:4 molar ratio of Sc(OTf)3 to
3-HQD. Naturally, with optimized conditions in hand, we examined a
set of aromatic aldehydes coupled with activated alkenes (methyl acrylate,
ethyl acrylate, and acrylonitrile). The experimental results are listed
in Table 3.
Table 2. MBH reactions of p-nitrobenzaldehyde (1.0 equiv.) with methyl acrylate
(3.0 equiv.) in the presence of Sc(OTf)3 and 3-HQD
Sc(OTf)3 3-HQD
Entry (mol %) (mol %)
Temperature Time Yield
(%)a
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH2Cl2
Toluene
H2O
DMF
THF=H2O (1:1)
DMF=H2O (1:1)
DMF
(ꢀC)
(h)
1
2
0
5
5
5
5
5
5
5
5
5
5
5
50
10
20
50
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
0
3
3
1
1
1
1
59
52
78
79
66
71
<10
84
66
62
44
88
3
4
5
6
7
8
9
10
11
12
1
50 min
1
1
3
DMF
40
50 min
aIsolated yield based on p-nitrobenzaldehyde.

1038
Y. Shang, D. Wang, and J. Wu
Table 3. Sc(OTf)3=3-HQD cocatalyzed the MBH reactiona
Entry
1
Products
Time (h)
8
Yield (%)b
73
2
3
4
9
9
70
73
30
36
5
36
23
6
7
8
9
6
79
74
82
8
4
50 min
92
(Continued )

Sc(OTf)3/3-HQD Catalyst for MBH Reaction
1039
Table 3. Continued
Entry
10
Products
Time (h)
1
Yield (%)b
88
11
10 min
98
12
13
14
3
4
88
88
90
1.5
15
16
17
1
1
88
88
92
40 min
aReaction conditions: 3.0 mmol of a,b-unsaturated ester, 1.0 mmol of aromatic
aldehydes, 5 mmol% of Sc(OTf)3, and 20 mmol% of Lewis base using DMF as
solvent.
bIsolated yield based on aromatic aldehyde.

1040
Y. Shang, D. Wang, and J. Wu
As shown in Table 3, all aromatic aldehydes were converted to their
corresponding MBH products in moderate to high yields in reaction
times as short as 10 min. It is worth mentioning that the system was tested
synthetically on various substrates and found to give good rate accelera-
tions with aromatic aldehydes with acceptor groups and lower rate accel-
erations with aromatic aldehydes with donor groups. Notable examples
from Table 3 include a fast reaction with 2-furaldehyde and acrylonitrile
(entry 17) and a very rapid reaction with p-nitrobenzaldehyde (entry 11).
Acrylamide is not a suitable substrate with 3-HQD; no reaction was
observed with it.
CONCLUSIONS
In conclusion, we have developed a new condition that accelerates the
MBH reaction. The novel catalytic system of a combination of Sc(OTf)3
and 3-HQD showed high catalytic activity for the MBH reaction.
EXPERIMENTAL
All chemicals and resin were obtained from commercial suppliers and
were used without further purification. Infrared (IR) spectra were
recorded on a Perkin-Elmer 983 Fourier transform infrared (FT-IR)
1
spectrometer, and H NMR spectra were made on a Bruker Avance
DMX 300 instrument. Mass spectral (MS) analyses were performed on
an HP-5973 spectrometer.
General Procedure for the Synthesis of 1–17
Aromatic aldehyde (1 mmol) was mixed with activated alkenes (3 mmol)
in a 25-mL flask. Sc(OTf)3 (5 mol%), 3-HQD (20 mol%), and DMF
(4 mL) were added to the mixture. The vessel was immersed in a pre-
heated oil bath and stirred vigorously until thin-layer chromatography
(TLC) and=or gas chromatography (GC) of the crude reaction mixture
indicated that the aromatic aldehyde had been completely consumed.
The reaction mixture was allowed to cool to room temperature, Et2O
was added to the reaction mixture, and the organic phase was
separated. The filtrate was concentrated, and the resulting residue was
purified by flash chromatography (hexane–ethyl acatate) to provide
the desired product.

Sc(OTf)3/3-HQD Catalyst for MBH Reaction
Data
1041
Methyl 2-[1-Hydroxy-1-(4-nitrophenyl)Methyl]Acrylate (Table 3, Entry 1)
1
A yellowish oil; H NMR (CDCl3, 300 MHz): d 3.46 (brs, 1H), 3.67 (s,
3H), 5.57 (d, H, J ¼ 6.52 Hz), 5.84 (s, 1H), 6.33 (s, 1H), 7.50 (d, 2H,
J ¼ 8.52 Hz), 8.12 (d, 2H, J ¼ 8.51 Hz); 13C NMR (CDCl3, 75 MHz):
d 51.86, 72.1, 123.25, 126.86, 127.02, 140.63, 147.04, 148.34, 166.02; IR
(CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(4-nitrophenyl)Methyl]Acrylate (Table 3, Entry 2)
A yellowish oil; 1H NMR (CDCl3, 300 MHz): d 1.32 (t, 3H, J ¼ 7.14 Hz),
3.46 (brs, 1H), 4.24 (q, 2H, J ¼ 7.14 Hz), 5.67 (d, H, J ¼ 6.15 Hz), 5.91 (s,
1H), 6.45 (s, 1H), 7.63 (d, 2H, J ¼ 8.64 Hz), 8.25 (d, 2H, J ¼ 8.64 Hz); 13
C
NMR (CDCl3, 75 MHz): d 13.63, 60.60, 65.36, 72.02, 123.17, 126.49,
140.94, 146.93, 148.59, 165.54; IR (CHCl3) 3485, 1720 cmꢁ1
.
2-[1-Hydroxy-1-(4-nitrophenyl)Methyl]Acrylonitrile (Table 3, Entry3)
A yellowish oil; 1H NMR (CDCl3, 300 MHz): d 2.98 (brs, 1H), 5.38 (d, 1H,
J ¼ 6.3 Hz), 6.04 (s, 1H), 6.13 (s, 1H), 7.54 (d, 2H, J ¼ 8.40Hz), 8.19 (d, 2H,
J ¼ 8.40Hz); 13C NMR (CDCl3, 75MHz): d 72.85, 116.02, 123.70, 125.05,
127.04, 130.78, 145.82, 147.60; IR (CHCl3) 3480, 1720cmꢁ1
.
Methyl 2-[1-Hydroxy-1-(2,4-dichlorophenyl)Methyl]Acrylate
(Table 3, Entry 4)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d3.52 (brs, 1H), 3.76 (s,
1H), 5.58 (d, 1H, J ¼ 6.87 Hz), 5.89 (s, 1H), 6.33 (s, 1H), 7.26 (d, 1H,
J ¼ 8.07 Hz), 7.36 (s, 1H), 7.48 (d, 1H, J ¼ 8.31 Hz); 13C NMR (CDCl3,
75 MHz): d 51.86, 68.54, 126.78, 128.82, 133.07, 136.63, 139.88, 144.66,
166.50; IR (CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(2,4-dichlorophenyl)Methyl]Acrylate
(Table 3, Entry 5)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 1.30 (t, 3H, J ¼ 6.40Hz),
3.58 (brs, 1H), 4.19 (q, 2H, J ¼ 6.40Hz), 5.19 (d, 1H, J ¼ 5.80Hz), 5.51
(s, 1H), 6.11 (s, 1H), 7.07 (d, 1H, J ¼ 8.31Hz), 7.11 (s, 1H), 7.21 (d, 1H,

1042
Y. Shang, D. Wang, and J. Wu
J ¼ 8.31Hz); 13C NMR (CDCl3, 75MHz): d 13.67, 60.85, 65.13, 68.36,
126.94, 128.79, 133.67, 140.27, 142.85, 165.30; IR (CHCl3) 3485, 1720cmꢁ1
.
2-[1-Hydroxy-1-(2,4-dichlorophenyl)Methyl]Acrylonitrile
(Table 3, Entry 6)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 3.12 (brs, 1H), 5.70 (s,
1H), 6.07 (s, 1H), 6.08 (s, 1H), 7.35 (d, 1H, J ¼ 7.74 Hz), 7.41 (s, 1H),
7.57 (d, 1H, J ¼ 7.74 Hz); 13C NMR (CDCl3, 75 MHz): d 69.75, 117.32,
123.64, 127.59, 128.58, 131.29, 134.62, 139.81; IR (CHCl3) 3480,
1720 cmꢁ1
.
Methyl 2-[1-Hydroxy-1-(4-chlorophenyl)Methyl]Acrylate
(Table 3, Entry 7)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 3.11 (brs, 1H), 3.74 (s,
1H), 5.52 (d, 1H, J ¼ 5.58 Hz), 5.83 (s, 1H), 6.34 (s, 1H), 7.28 (d, 2H,
J ¼ 8.41 Hz), 7.33 (d, 2H, J ¼ 8.37 Hz); 13C NMR (CDCl3, 75 MHz):
d 51.74, 72.38, 120.64, 127.61, 129.71, 132.12, 138.41, 144.65, 165.11;
IR (CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(4-chlorophenyl)Methyl]Acrylate (Table 3, Entry 8)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d1.27 (t, 3H, J ¼ 7.07 Hz),
3.34 (brs, 1H), 4.16 (q, 2H, J ¼ 6.96 Hz), 5.51 (d, 1H, J ¼ 5.37 Hz), 5.83 (s,
1H), 6.34 (s, 1H), 7.31 (d, 2H, J ¼ 8.47 Hz), 7.38 (d, 2H, J ¼ 8.47 Hz);
13C NMR (CDCl3, 75 MHz): 1720 cmꢁ1
.
2-[1-Hydroxy-1-(4-chlorophenyl)Methyl]Acrylonitrile (Table 3, Entry 9)
A colorless oil; 1H NMR (CDCl3, 300 MHz): d 3.57 (brs, 1H), 5.20 (d, 1H,
J ¼ 6.74 Hz), 5.99 (s, 1H), 6.05 (s, 1H), 7.27 (d, 2H, J ¼ 8.41 Hz), 7.34 (d,
2H, J ¼ 8.37 Hz); 13C NMR (CDCl3, 75 MHz): d 72.96, 116.48, 125.50,
127.59, 128.69, 130.26, 134.27, 137.33; IR (CHCl3) 3480, 1720 cmꢁ1
.
Methyl 2-[1-Hydroxy-1-(phenyl) Methyl] Acrylate (Table 3, Entry 10)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 3.19 (brs, 1H), 3.71 (s,
3H), 5.54 (d, 1H, J ¼ 6.18 Hz), 5.83 (s, 1H), 6.32 (s, 1H), 7.27–7.33 (m,

Sc(OTf)3/3-HQD Catalyst for MBH Reaction
1043
5H); 13C NMR (CDCl3, 75 MHz): d 51.63, 72.79, 125.76, 126.27, 127.49,
128.08, 140.93, 141.60, 166.42; IR (CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(phenyl)Methyl]Acrylate (Table 3, Entry 11)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 2.96 (brs, 1H), 5.30 (d,
1H, J ¼ 5.10 Hz), 6.09 (s, 1H), 6.14 (s, 1H), 6.35 (d, 1H, J ¼ 4.98 Hz),
6.37 (d, 1H, J ¼ 4.72 Hz), 7.39 (d, 1H, J ¼ 4.50 Hz); 13C NMR (CDCl3,
75 MHz): d 74.31, 108.34, 110.47, 117.25, 123.61, 131.36, 143.20,
154.61; IR (CHCl3) 3485, 1720 cmꢁ1
.
2-[1-Hydroxy-1-(phenyl)Methyl]Acrylonitrile (Table 3, Entry 12)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 2.62 (brs, 1H), 5.52 (d,
1H, J ¼ 5.36 Hz), 6.01 (s, 1H), 6.09 (s, 1H), 7.36–7.41 (m, 5H); 13C
NMR (CDCl3, 75 MHz): d 73.85, 116.59, 125.86, 126.20, 128.62,
128.65, 129.51, 138.83; IR (CHCl3) 3480, 1720 cmꢁ1
.
Methyl 2-[1-Hydroxy-1-(furyl)Methyl]Acrylate (Table 3, Entry 13)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 3.31 (brs, 1H), 3.73 (s,
3H), 5.56 (d, 1H, J ¼ 4.92 Hz), 5.93 (s, 1H), 6.22 (s, 1H), 6.30 (d, 1H,
J ¼ 5.12 Hz), 6.36 (d, 1H, J ¼ 4.99 Hz), 7.34 (d, 1H, J ¼ 5.31 Hz); 13C
NMR (CDCl3, 75 MHz): d 52.31, 74.10, 108.29, 110.69, 122.74, 140.31,
154.28; IR (CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(furyl)Methyl]Acrylate (Table 3, Entry 14)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 1.23 (t, 3H, J ¼ 7.17 Hz),
3.70 (brs, 1H), 4.16 (q, 2H, J ¼ 7.18 Hz), 5.55 (d, 1H, J ¼ 6.01 Hz), 5.93
(d, 1H, J ¼ 2.67 Hz), 6.18 (d, 1H, J ¼ 3.21 Hz), 6.26 (d, 1H, J ¼ 2.83 Hz),
6.33 (d, 1H, J ¼ 2.71 Hz), 7.31 (d, 1H, J ¼ 2.05 Hz); 13C NMR (CDCl3,
75 MHz): d13.62, 60.60, 66.29, 106.74, 109.98, 125.90, 139.50, 141.86,
153.98, 165.65; IR (CHCl3) 3485, 1720 cmꢁ1
.
2-[1-Hydroxy-1-(furyl)Methyl]Acrylonitrile (Table 3, Entry 15)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 2.96 (brs, 1H), 5.30 (d,
1H, J ¼ 5.10 Hz), 6.09 (s, 1H), 6.14 (s, 1H), 6.35 (d, 1H, J ¼ 4.98 Hz),

1044
Y. Shang, D. Wang, and J. Wu
6.37 (d, 1H, J ¼ 4.72 Hz), 7.39 (d, 1H, J ¼ 4.50 Hz); 13C NMR (CDCl3,
75 MHz): d 74.31, 108.34, 110.47, 117.25, 123.61, 131.36, 143.20,
154.61; IR (CHCl3) 3480, 1720 cmꢁ1
.
Methyl 2-[1-Hydroxy-1-(4-methoxyphenyl)Methyl]Acrylate
(Table 3, Entry 16)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 2.91 (brs, 1H), 3.76 (s,
3H), 3.84 (s, 3H), 5.57 (d, 1H, J ¼ 4.79 Hz), 5.88 (s, 1H), 6.36 (s, 1H),
6.90 (d, 2H, J ¼ 8.64 Hz), 7.32 (d, 2H, J ¼ 8.58 Hz); 13C NMR (CDCl3,
300 MHz): d 52.30, 55.91, 74.21, 114.35, 122.96, 128.32, 133.62, 140.67,
159.30, 167.38; IR (CHCl3) 3490, 1715 cmꢁ1
.
Ethyl 2-[1-Hydroxy-1-(4-methoxyphenyl)Methyl]Acrylate
(Table 3, Entry 17)
1
A colorless oil; H NMR (CDCl3, 300 MHz): d 1.23 (t, 3H, J ¼ 7.14 Hz),
3.24 (brs, 1H), 3.85 (s, 3H), 4.14 (q, 2H, J ¼ 6.93 Hz), 5.50 (d, 1H,
J ¼ 6.20 Hz), 5.85 (s, 1H), 6.31 (s, 1H), 6.86 (d, 2H, J ¼ 8.61 Hz), 7.27
(d, 2H, J ¼ 8.58 Hz); 13C NMR (CDCl3, 75 MHz): d 13.7, 54.89, 60.53,
72.36, 113.41, 124.99, 127.57, 133.21, 142.06, 158.81, 166.02; IR (CHCl3)
3485, 1720 cmꢁ1
.
ACKNOWLEDGMENTS
The authors thank the National Natural Science Foundation of China
(Grant No. 20872001) and the Natural Science Foundation of Education
Administration of Anhui Province (KJ2008A064).
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Sc(OTf)3/3-HQD Catalyst for MBH Reaction
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