DABCO-catalyzed green synthesis of 2-Hydroxy-1,4-diones via direct aldol reaction of arylglyoxals in water

Article abstract of DOI:10.5012/jkcs.2013.57.2.252

A green and simple method to synthesize of 1,4-diketones via aldol reaction of arylglyoxals and ketones such as 1-(4-methoxyphenyl)-2-propanone, deoxybenzoin and substituted acetophenones in the presence of a catalytic amount of DABCO in water at room temperature has been reported. Corresponding 2-hydroxy-1,4-diones were obtained in moderate to high yields with simple separation of obtained solid from reaction mixture and recrystallization.

Full text of DOI:10.5012/jkcs.2013.57.2.252

Journal of the Korean Chemical Society
2013, Vol. 57, No. 2
Printed in the Republic of Korea
http://dx.doi.org/10.5012/jkcs.2013.57.2.252
DABCO-Catalyzed Green Synthesis of 2-Hydroxy-1,4-diones via Direct Aldol
Reaction of Arylglyoxals in Water
†,
*
Mahnaz Saraei*, Bagher Eftekhari-Sis , and Sakineh Mozaffarnia
†
Department of Chemistry, Payame Noor University, P. O. Box. 19395-3697, Tehran, Iran.
*
E-mail: m_saraii@yahoo.com
†
Department of Chemistry, University of Maragheh, P. O. Box. 55181-83111, Maragheh, Iran.
*
E-mail: eftekharisis@maragheh.ac.ir
(Received November 27, 2012; Accepted March 13, 2013)
ABSTRACT. A green and simple method to synthesize of 1,4-diketones via aldol reaction of arylglyoxals and ketones such
as 1-(4-methoxyphenyl)-2-propanone, deoxybenzoin and substituted acetophenones in the presence of a catalytic amount of
DABCO in water at room temperature has been reported. Corresponding 2-hydroxy-1,4-diones were obtained in moderate to
high yields with simple separation of obtained solid from reaction mixture and recrystallization.
Key words: 1,4-Diketones, Aldol reaction, Arylglyoxals, DABCO, Green chemistry
11
or masked acyl anions and their equivalents. Also, the
INTRODUCTION
preparation of 1,4-dicarbonyl compounds were carried
12
out by the classic utilization of α-halo ketones, by appli-
Because of water is one of the most abundant and cheap
solvents, and also makes the reactions environmentally
13
cation of the Stetter reagent, thiazolium salts in the pres-
1
amenable, much safer and easier to handle, the organic
14
ence of a tertiary amine, or 1,3-dithiane derivatives.
15
reactions in aqueous media have attracted much attention
Recently, we have reviewed the application of arylgly-
2
in synthetic organic chemistry. Also, reactions in water
oxals (aromatic α-ketoaldehyds) in synthesis of hetero-
16
cyclic compounds, that encouraged us to work on aldol
exhibit interesting reactivity and selectivity, which are dif-
ferent from conventional organic solvents.
reaction of arylglyoxals to prepare 1,4-dicarbonyl com-
pounds.
The routes for formation of C−C bonds are the most
important topics in synthetic organic chemistry. The aldol
reaction is one of the most powerful C−C bond-forming
However, aldol reaction with some α-dicarbonyl com-
17
pounds such as benzil, isatin and ethyl phenylglyoxalate
3
reactions in organic synthesis, leading to the β-hydrox-
to synthesize of 1,4-dicarbonyl compounds were previ-
18
ously reported, as the best of our knowledge, there is one
ycarbonyl structural units, which are found in several bio-
logically active compounds, such as macrolide antibiotics
report on aldol reaction of arylglyoxals in the literature
using expensive chiral ligand with limited scope of prod-
ucts, in which trimethylsilyl enols of ketones were used in
4
and anti-cancer drugs, and also are important building
blocks in the synthesis of polyfunctional compounds and
3d,5
19
natural products.
CH2Cl2.
Additionally, 1,4-dicarbonyl compounds are versatile
precursors for the synthesis of substituted cyclopenten-
Herein, we wish to report the direct aldol reaction of dif-
ferent ketones such as 1-(4-methoxyphenyl)-2-propanone,
deoxybenzoin and substituted acetophenones with arylg-
lyoxals in water to produce 2-hydroxy-1,4-diketones in
the presence of a catalytic amount of DABCO.
6
6g−i
ones, such as jasmones, cuparenones, and prostag-
6c
6j−l
landins, and also various heterocyclic compounds, for
example, furan, thiophene, pyrrole, and pyridazine deriv-
7
atives. Thus the development of the synthetic methods of
the 1,4-diketones have a significant impact on organic
chemistry. A number of methods have already been reported
RESULTS AND DISCUSSION
8
for the preparation of 1,4-diketone derivatives, and among
We first studied the aldol reaction of 1-(4-methoxyphe-
them, most widely used approach is the Michael addition
nyl)propan-2-one 1a with phenylglyoxal hydrate 2a, which
20
to α,β-unsaturated ketones of either unmasked acyl anions
were prepared by oxidation of acetophenone using SeO2,
9
such as acyllithium, and acyl-transition metal complexes,
10
in water in the presence of different tertiary amines such
-252-

DABCO-Catalyzed Green Synthesis of 2-Hydroxy-1,4-diones via Direct Aldol Reaction of Arylglyoxals in Water
253
Scheme 2. Reaction of 1b with arylglyoxal hydrates in water in
the presence of DABCO.
Scheme 1. Reaction of 1a with phenylglyoxal hydrate 2a in water.
Table 1. Aldol reaction of 1a and 1b with arylglyoxal hydrates 2
a
in the presence of DABCO in water.
Ketone
[1]
Product Yield
c
Ar' [2]
syn/anti
b
[3]
3a
3b
3c
3d
3e
3f
(%)
95
77
84
82
74
72
70
82
80
1a
1a
1a
1a
1a
1a
1b
1b
1b
Ph [2a]
>99/1
>99/1
>99/1
67/33
67/33
64/36
>99/1
>99/1
65/35
4-ClC6H4 [2b]
4-BrC6H4 [2c]
4-MeOC6H4 [2d]
3-MeOC6H4 [2e]
3,4-(MeO)2C6H3 [2f]
4-ClC6H4 [2b]
3g
3h
3i
4-BrC6H4 [2c]
4-MeOC6H4 [2d]
a
b
Reaction time was 24 h, except in the case of 3i which was 48 h.
Fig. 1. ORTEP representation of 3a with 45% ellipsoid proba-
Yields refer to isolated products by simple filtration of the reaction
21
bility.
mixture.
c
1
Anti/syn ratio was determined using H NMR spectroscopic analy-
sis of the crude reaction mixture.
as Et3N, DMAP and DABCO, and also NaOH at room
temperature to give 2-hydroxy-3-(4-methoxyphenyl)-1-
phenylpentane-1,4-dione 3a (Scheme 1). When DABCO
was used, 2-hydroxy-1,4-dione 3a was obtained in 95%
As shown in Table 1, electron-withdrawing substituted
phenylglyoxals such as 4-Cl and 4-Br worked as well as
electron-donating substituted phenylglyoxals such as 3-
MeO, 4-MeO and 3,4-(MeO)2 in DABCO-catalyzed aldol
reaction in water. Phenyl-, 4-Clphenyl- and 4-Br-phenylg-
lyoxals underwent aldol reaction with excellent diastere-
oselectivity (3a−c and 3g,h), while electron-donating substituted
phenylglyoxals afforded corresponding 2-hydroxy-1,4-
diketones 3d−f and 3i as a mixture of two stereoisomers.
1
yield as only syn isomer, determined using H NMR spec-
troscopy. The crystal structure of the compound 3a (Fig.
21
1), which was synthesized by the similar procedure,
22
23
was reported by K. Harms, which is consistent with syn
isomer.
Aldol reactions of 1a with different substituted phe-
nylglyoxal hydrates 2b−f were also investigated. The
reactions were carried out by addition of DABCO to a
mixture of 1a (0.5 mmol) and 2 (0.05 mmol) in water and
stirred at room temperature for appropriate time. The cor-
responding 2-hydroxy-1,4-diones 3b−f were obtained in
good to high yields. Also the aldol reaction of deoxyben-
zoin 1b was conducted with different arylglyoxals 2 under
the same conditions, and the corresponding 2-hydroxy-
1,4-diones 3g−i were obtained in good to high yields
(Scheme 2). The results are summarized in Table 1. The
As shown in Fig. 2, the syn/anti ratio was determined by
1
H NMR, using the intensity of the H for two isomers.
a
3
The coupling constant ( JHa,Hb) for signal of the anti-iso-
mer is higher than that of the syn-isomer. According to the
1
H NMR spectrum, the H signal for the syn-isomer has a
a
higher δ value than that for the anti-isomer. For instance,
1
in the H NMR spectra of 2-hydroxy-1,3-bis(4-methox-
yphenyl)pentane-1,4-dione (3d), the signal at δ = 5.78 ppm
3
( JHa,Hb = 4.4 Hz) is contributed by the syn-isomer, while
1
products were characterized using FT-IR, H NMR and
3
the one at 5.28 ppm ( JHa,Hb = 5.6 Hz) is contributed by the
13
C NMR spectroscopy.
anti-isomer.
2013, Vol. 57, No. 2

254
Mahnaz Saraei, Bagher Eftekhari-Sis, and Sakineh Mozaffarnia
Table 2. Aldol reaction of acetophenones 4 with arylglyoxal
hydrates 2 in the presence of DABCO in water at room temper-
ature (See also Scheme 4)
a
Ar' [2]
2a
Ar [4]
4-ClC6H4
4-BrC6H4
4-NO2C6H4
Ph
Product (5) Time (h) Yield (%)
5a
5b
5c
5d
5e
5f
28
15
24
30
48
58
24
48
48
192
18
33
59
25
47
67
56
53
64
59
60
55
88
68
2a
2a
2b
2b
2b
2b
2c
4-ClC6H4
4-BrC6H4
2-thienyl
Ph
5g
5h
5i
2c
4-ClC6H4
4-BrC6H4
4-NO2C6H4
2-furyl
2c
5j
2c
5k
5l
2c
a
Yields refer to isolated products by simple filtration of the reaction
mixture and washing with warm water and cold EtOH to remove
unreacted arylglyoxals and acetophenones, respectively.
1
Fig. 2. Identification of anti and syn isomer by H NMR.
amount of DABCO. The reaction mixture was solidified
after appropriate time. The obtained solid was filtered off
and washed with hot water to remove arylglyoxal and ace-
tophenone residue. The results are summarized in Table 2.
As shown in Table 2, different 4were subjected to DABCO-
catalyzed aldol reaction with 2 to give corresponding 2-
hydroxy-1,4-diones 5 in 25−88% yields. Also, heterocy-
clic methyl ketones such as 2-furyl and 2-thienyl methyl
ketones underwent aldol reaction in water at room tem-
perature to afford corresponding 1,4-diones 5g,l in good
yields. The structure of products were established using
Scheme 3. Chemoselectivity of the aldol reaction of 1a toward
phenylglyoxal, in preference to benzaldehyde.
1 13
FT-IR, H NMR and C NMR.
Another characteristic feature of the present protocol is
the high chemoselectivity of the aldol reaction toward
phenylglyoxal, in preference to benzaldehyde as shown in
Scheme 3. When aldol reaction of phenylglyoxal with 1a
in the presence of 1 equiv. of benzaldehyde was carried
out under same conditions, only 3a was isolated and ben-
zaldehyde was recovered without changes.
Attempts to aldol reaction of arylglyoxals with ali-
phatic ketones such as acetone and cyclohexanone under
the same conditions were failed and a mixture of products
was obtained.
CONCLUSION
The results encouraged us to work on the aldol reaction
of acetophenone derivatives 4 with arylglyoxal hydrates 2
(Scheme 4). The reactions were conducted by stirring of a
mixture of acetophenones and arylglyoxal hydrates in
water at room temperature in the presence of catalytic
In conclusion, a new green and simple methodology for
construction of 1,4-diketone along with 2- and 3-hydroxy
structural motifs was developed. Reactions were carried
out in water at room temperature using DABCO as cat-
alyst. Ketones such as 1a,b worked well in aldol reaction
in water and afforded corresponding 2-hydroxy-1,4-diones
in good to high yields. Electron-withdrawing substituted
phenylgyloxals afforded the 1,4-diones with excellent syn
selectivity, while arylglyoxals with electron-donating substit-
uents gave corresponding 1,4-diones as a two diastereoi-
somers with ratio of about 2/1 of syn/anti. Also, acetophenone
Scheme 4. DABCO-catalyzed aldol reaction of acetophenones 4
with 2 in water at room temperature.
Journal of the Korean Chemical Society

DABCO-Catalyzed Green Synthesis of 2-Hydroxy-1,4-diones via Direct Aldol Reaction of Arylglyoxals in Water
255
deivatives worked well in aldol reaction with arylglyox-
als in water.
MHz, CDCl3) δ = 209.6, 199.0 (C=O), 159.5, 139.9, 133.4,
130.5, 130.3, 128.7, 126.1, 114.5, 76.1, 59.8, 55.3, 30.2
ppm. Anal. Calcd for C18H17ClO4 (332.78): C 64.97, H
5.15; Found: C 64.90, H 5.30%.
EXPERIMENTAL
1-(4-Bromophenyl)-2-hydroxy-3-(4-methoxyphenyl)
pentane-1,4-dione (3c)
All chemicals were purchased and used without any fur-
ther purification. NMR spectra were recorded at 400 MHz
for proton and at 100 MHz for carbon nuclei in CDCl3 or
DMSO-d6. Most of compounds were new and characterized
by their spectroscopic data (FT-IR, NMR and elemental
analysis).
o
White solid, m.p. 118.5−120.1 C. FT-IR (KBr) ν = 3335
(br., O−H), 3069, 2941 (C−H), 1695 (C=O), 1578 (C=C),
−1 1
1244 (C−O), 579 (C−Br) cm . H NMR (400 MHz, CDCl3) δ
= 7.72−7.75 (m, 2H, CHAr), 7.53−7.56 (m, 2H, CHAr), 7.19−
7.22 (m, 2H, CHAr), 6.83−6.86 (m, 2H, CHAr), 5.22−5.28
3
(m, 1H, CH−O) 4.33 (m, br., 1H, OH), 4.20 (d, JH,H = 5.6
General Procedure of the Aldol Reaction
Hz, 1H, CH), 3.80 (s, 3H, OCH3), 2.20 (s, 3H, CH3) ppm.
13
To a mixture of arylglyoxal 2 (0.55 mmol) and ketone 1
or 4 (0.5 mmol) in 3−5 mL water, was added 0.02 g DABCO
and stirred at room temperature. The progress of the reac-
tion was monitored by TLC (n-hexane/ethyl acetate; 7/3).
After completion of the reaction, the products were iso-
lated as solid from reaction mixture, which was filtered off
and washed with hot water and cold EtOH to remove unre-
acted arylglyoxals and ketones, respectively. All obtained
products are almost pure, but further purification for ele-
mental analysis were carried out by recrystallization from
EtOH.
C NMR (100 MHz, CDCl3) δ = 209.6, 199.3 (C=O), 159.5,
133.8, 131.7, 130.6, 130.3, 128.6, 126.1, 114.5, 76.1, 59.8,
55.3, 30.1 ppm. Anal. Calcd for C18H17BrO4 (377.23): C
57.31, H 4.54; Found: C 56.76, H 4.27%.
2-Hydroxy-1,3-bis(4-methoxyphenyl)pentane-1,4-
dione (3d)
Syn/anti = 67/33. Yellow oil, FT-IR (KBr) ν = 3442 (br.,
O−H), 3040, 2943 (C−H), 1706, 1670 (C=O), 1602 (C=C),
−1
1255 (C−O) cm . 1H NMR (400 MHz, CDCl3) δ = 7.82−
7.92 (2×m, 2H, CHAr), 6.79−7.21 (3×m, 6H, CHAr), 5.78
3 3
(d, JH,H = 4.4 Hz, 0.67H, CH−O, anti), 5.28 (d, JH,H = 5.6
3
Hz, 0.33H, CH−O, syn), 4.16 (d, JH,H = 5.6 Hz, 0.33H,
2-Hydroxy-3-(4-methoxyphenyl)-1-phenylpentane-1,4-
dione (3a)
3
CH, syn), 4.02 (d, JH,H = 4.4 Hz, 0.67H, CH, anti), 3.84-
o
White solid, m.p. 95−95.3 C. FT-IR (KBr) ν = 3316
3.90 [2×S: (3.90, ~2H, anti; 3.84, ~1H, syn), 3H, OCH3],
3.76-3.79 [2×S: (3.79, ~2H, anti; 3.76, ~1H, syn), 3H,
OCH3], 2.12−2.17 [2×S: (2.17, ~1H, syn; 2.12, ~2H, anti),
(O−H), 3068, 2891 (C−H), 1712, 1674 (C=O), 1645
−1 1
(C=C), 1245 (C−O) cm . H NMR (500 MHz, CDCl3): δ
3 4
= 7.90 (dd, JH,H = 7.9 Hz, JH,H = 0.8 Hz, 2H, CHAr), 7.66
13
3H, CH3] ppm. C NMR (100 MHz, CDCl3) δ = 209.3,
3
(m, 1H, CHAr), 7.53 (t, JH,H = 7.9 Hz, 2H, CHAr), 7.01 (d,
206.6, 198.4, 198.2 (C=O), 164.1, 163.8, 159.4, 159.3,
132.2, 131.4, 131.1, 130.3, 127.8, 127.0, 126.5, 125.2,
114.4, 114.17, 114.16, 113.7, 75.5, 72.5, 61.9, 60.3, 55.6,
55.5, 55.3, 55.2, 30.4, 29.2 ppm. Anal. Calcd for C19H20O5
(328.36): C 69.50, H 6.14; Found: C 69.83, H 6.21%.
2-Hydroxy-1-(3-methoxyphenyl)-3-(4-methoxyphe-
nyl)pentane-1,4-dione (3e)
3
3
JH,H = 9.5 Hz, 2H, CHAr), 6.86 (d, JH,H = 9.6 Hz, 2H,
3 3
CHAr), 5.85 (d, JH,H = 4.0 Hz, 1H, CH−O), 4.03 (d, JH,H
=
4.1 Hz, 1H, CH), 3.82 (s, 3H, OCH3), 3.26 (s, br., 1H, OH,
13
Exchange with D2O), 2.14 (s, 3H, CH3) ppm. C NMR
(125 MHz, CDCl3): δ = 206.8 (C=O), 200.4 (C=O), 159.9,
134.8, 134.2, 131.5, 129.3, 129.0, 125.4, 114.6, 73.3, 62.1,
55.6, 29.5 ppm. Anal. Calcd for C18H18O4 (298.33): C
72.47, H 6.08; Found: C 72.51, H 6.10%.
Syn/anti = 67/33. Yellow oil, FT-IR (KBr) ν = 3504 (br.,
O−H), 3098, 2947 (C−H), 1693 (br., C=O), 1596 (C=C),
−1 1
1253 (C−O) cm . H NMR (400 MHz, CDCl3) δ = 6.78−
1-(4-Chlorophenyl)-2-hydroxy-3-(4-methoxyphenyl)
pentane-1,4-dione (3b)
3
7.50 (9×m, 8H, CHAr), 5.82 (d, JH,H = 4.0 Hz, 0.67H,
o
White solid, m.p. 119−123 C. FT-IR (KBr) ν = 3355
3
CH−O, anti), 5.30 (d, JH,H = 5.6 Hz, 0.33H, CH−O, syn),
3 3
4.19 (d, JH,H = 5.6 Hz, 0.33H, CH, syn), 4.04 (d, JH,H =
(br., O−H), 3071, 2943 (C−H), 1716, 1685 (C=O), 1583
−1 1
(C=C), 1244 (C−O), 601 (C−Cl) cm . H NMR (400
4.0 Hz, 0.67H, CH, anti), 3.83−3.87 [2×S: (3.87, ~2H,
anti; 3.83, ~1H, syn), 3H, OCH3], 3.78−3.81 [2×S: (3.81,
~2H, anti; 3.78, ~1H, syn), 3H, OCH3], 2.13−2.17 [2×S:
3
MHz, CDCl3) δ = 7.82 (d, JH,H = 8.8 Hz, 2H, CHAr), 7.37
3 3
(d, JH,H = 8.4 Hz, 2H, CHAr), 7.20 (d, JH,H = 8.8 Hz, 2H,
3 3
CHAr), 6.84 (d, JH,H = 8.8 Hz, 2H, CHAr), 5.23 (d, JH,H
13
(2.17, ~1H, syn; 2.13, ~2H, anti), 3H, CH3] ppm. C NMR
=
3
5.2 Hz, 1H, CH−O), 4.20 (d, JH,H = 5.2 Hz, 1H, CH), 3.80
(100 MHz, CDCl3) δ = 209.3, 206.4, 200.0, 199.8 (C=O),
13
(s, 3H, OCH3), 2.20 (s, 3H, CH3) ppm. C NMR (100
160.0, 159.6, 159.5, 159.4, 136.3, 135.6, 131.1, 130.3,
2013, Vol. 57, No. 2

256
Mahnaz Saraei, Bagher Eftekhari-Sis, and Sakineh Mozaffarnia
3 3
5.13 (d, JH,H = 6.0 Hz, 1H, CH), 4.53 (d, JH,H = 7.6 Hz,
130.0, 129.4, 126.4, 125.0, 121.6, 121.1, 120.3, 120.2,
114.4, 114.2, 113.0, 112.9, 75.9, 72.9, 61.7, 60.3, 55.5,
55.4, 55.3, 55.2, 30.2, 29.1 ppm. Anal. Calcd for C19H20O5
(328.36): C 69.50, H 6.14; Found: C 68.89, H 5.78%.
1-(3,4-Dimetoxyphenyl)-2-hydroxy-3-(4-metoxyphe-
nyl)pentane-1,4-dione (3f)
1
1H, OH) ppm. H NMR (400 MHz, CDCl3+drops of D2O)
3 3
δ = 7.97 (d, JH,H = 8.8 Hz, 2H, CHAr), 7.77 (d, JH,H = 8.8
Hz, 2H, CHAr), 7.51−7.56 (m, 3H, CHAr), 7.41−7.44 (m,
3
2H, CHAr), 7.19−7.33 (m, 5H, CHAr), 5.43 (d, JH,H = 5.6
3
13
Hz, 1H, CHO), 5.13 (d, JH,H = 5.6 Hz, 1H, CH) ppm. C
NMR (100 MHz, CDCl3) δ = 200.5, 199.5 (C=O), 136.2,
134.5, 133.9, 133.6, 131.7, 130.7, 129.2, 129.0, 128.9,
128.7, 128.6, 128.0, 58.4, 55.6, 31.0 ppm. Anal. Calcd for
C22H17BrO3 (409.27): C 64.56, H 4.19; Found: C 64.01, H
4.72%.
Syn/anti = 64/36. Yellow oil, FT-IR (KBr) ν = 3511 (br.,
O−H), 3093, 2941 (C−H), 1712, 1672 (C=O), 1598 (C=C),
−1 1
1265 (C−O) cm . H NMR (400 MHz, CDCl3) δ = 7.51-
3 4
7.61 [2×dd: 7.59 (dd, JH,H = 8.4 Hz, JH,H = 2.0 Hz), 7.50
3 4
(dd, JH,H = 8.4 Hz, JH,H = 2.0 Hz) 1H, CHAr], 7.39-7.41
3
(m, 1H, CHAr), 7.12−7.20 [2×d: 7.20 (d, JH,H = 8.8 Hz),
2-Hydroxy-1-(4-methoxyphenyl)-3,4-diphenylbutane-
1,4-dione (3i)
3
7.12 (d, JH,H = 8.8 Hz), 1H, CHAr], 6.93−7.02 [2×d: 7.02
3 3
(d, JH,H = 8.8 Hz), 6.93 (d, JH,H = 8.4 Hz), 2H, CHAr],
Syn/anti = 65/35. White solid. FT-IR (KBr) ν = 3471 (O−
H), 3064, 2952 (C−H), 1670 (C=O), 1591 (C=C), 1267
3
6.79−6.85 (m, 2H, CHAr), 5.78 (d, JH,H = 4.4 Hz, 0.64H,
3
CH−O, anti), 5.29 (d, JH,H = 5.6 Hz, 0.36H, CH−O, syn),
−1
1
(C−O) cm . H NMR (400 MHz, CDCl3) δ = 7.96−7.99
(m, 2H, CHAr), 7.86−7.90 (m, 2H, CHAr), 7.16−7.55
3 3
4.18 (d, JH,H = 5.6 Hz, 0.36H, CH, syn), 4.04 (d, JH,H
=
3
(7×m, 8H, CHAr), 6.83−6.98 [2×d: (6.98, JH,H = 9.2 Hz;
4.4 Hz, 0.64H, CH, anti), 3.88−3.97 (3×s, 6H, OCH3),
3.73−3.79 [2×S: (3.79, ~1.9H, anti; 3.73, ~1.1H, syn), 3H,
OCH3], 2.12−2.17 [2×S: (2.17, ~1.1H, syn; 2.12, ~1.9H,
3
6.83, JH,H = 8.8 Hz), 2H, CHAr), 5.84 (m, br., 0.65H, CH−
3
O, anti), 5.53 (m, br., 0.35H, CH−O, syn), 5.09 (d, JH,H
=
13
anti), 3H, CH3] ppm. C NMR (100 MHz, CDCl3) δ =
3
6.4 Hz, 0.35H, CH, syn), 5.05 (d, JH,H = 5.2 Hz, 0.65H,
CH, anti), 4.45 (m, br., 0.35H, OH, syn), 3.86−3.92 [2×S:
(3.92, ~2H, anti; 3.86, ~1H, syn), 3H, OCH3], 3.03 (s, br.,
209.5, 206.7, 198.4, 198.2 (C=O), 159.4, 159.36, 153.9,
153.6, 149.3, 148.8, 131.1, 130.4, 127.9, 127.2, 126.4, 125.3,
124.1, 123.4, 114.4, 114.2, 110.9, 110.7, 110.3, 109.9,
75.5, 72.5, 62.1, 60.3, 56.2, 56.1, 55.9, 55.3, 55.2, 50.1,
30.3, 29.2 ppm. Anal. Calcd for C20H22O6 (358.39): C
67.03, H 6.19; Found: C 66.51, H 6.28%.
13
0.65H, OH, anti) ppm. C NMR (100 MHz, CDCl3) δ =
200.0, 198.7, 198.0, 197.9 (C=O), 164.1, 163.8, 136.5, 136.0,
134.1, 133.4, 133.1, 131.6, 131.4, 129.7, 129.1, 129.0, 128.97,
128.9, 128.6, 128.5, 127.9, 127.8, 127.5, 114.1, 113.6, 76.3,
73.6, 57.5, 56.2, 55.6, 55.5 ppm. Anal. Calcd for C23H20O4
(360.40): C 76.65, H 5.59; Found: C 76.09, H 5.72%.
4-(4-Chlorophenyl)-2-hydroxy-1-phenylbutane-1,4-
dione (5a)
1-(4-Chlorophenyl)-2-hydroxy-3,4-diphenylbutane-
1,4-dione (3g)
o
White solid, m.p. 176.8−179.6 C. FT-IR (KBr) ν = 3367
(br., O−H), 3060, 2893 (C−H), 1670 (C=O), 1583 (C=C),
−1 1
1199 (C−O), 694 (C−Cl) cm . H NMR (400 MHz, CDCl3)
o
White solid, m.p. 132.5−136 C. FT-IR (KBr) ν = 3743
3 3
δ = 7.97 (d, JH,H = 8.0 Hz, 2H, CHAr), 7.85 (d, JH,H = 8.8
(O−H), 3061 (C−H), 1681 (C=O), 1552 (C=C), 1195 (C−O),
−1 1
651 (CCl) cm . H NMR (400 MHz, CDCl3) δ = 8.01 (d,
Hz, 2H, CHAr), 7.52−7.56 (m, 1H, CHAr), 7.41−7.44 (m,
3
2H, CHAr), 7.19−7.36 (m, 7H, CHAr), 5.44−5.48 (dd, JH,H
3
3
JH,H = 8.4 Hz, 2H, CHAr), 7.91 (d, JH,H = 8.4 Hz, 2H,
3
= 5.6, 9.2 Hz, 1H, CH−O), 5.13 (d, JH,H = 5.6 Hz, 1H,
3 3
CHAr), 7.66 (t, JH,H = 7.2 Hz, 1H, CHAr), 7.54 (t, JH,H =
3
13
3
7.6 Hz, 2H, CHAr), 7.46 (d, JH,H = 8.8 Hz, 2H, CHAr), 5.69
(s, br., 1H, OH), 4.05 (m, 1H, CH−O), 3.33−3.45 (m, 2H,
CH), 4.53 (d, JH,H = 9.2 Hz, 1H, OH) ppm. C NMR (100
MHz, CDCl3) δ = 200.4, 199.3 (C=O), 139.9, 136.2, 134.5,
133.6, 133.5, 130.7, 129.2, 129.0, 128.9, 128.7, 128.0, 59.5,
55.7, 31.3 ppm. Anal. Calcd for C22H17ClO3 (364.82): C
72.43, H 4.70; Found: C 72.50, H 4.80%.
1
CH2) ppm. H NMR (400 MHz, DMSO-d6) δ = 8.03 (d,
3
3
JH,H = 7.2 Hz, 2H, CHAr), 8.00 (d, JH,H = 8.4 Hz, 2H,
3 3
CHAr), 7.67 (t, JH,H = 7.2 Hz, 1H, CHAr), 7.62 (d, JH,H
=
3
8.4 Hz, 2H, CHAr), 7.56 (t, JH,H = 7.6 Hz, 2H, CHAr), 5.85
1-(4-Bromophenyl)-2-hydroxy-3,4-diphenylbutane-
1,4-dione (3h)
3
(d, JH,H = 7.6 Hz, 1H, OH), 5.43−5.48 (m, 1H, CH−O),
o
White solid, m.p. 180−184.5 C. FT-IR (KBr) ν = 3361
3
3.35−3.59 [2×dd: 3.54−3.59 (dd, JH,H = 6.8, 17.2 Hz, 1H,
3
CH2), 3.35−3.41 (dd, JH,H = 6.4, 17.2 Hz, 1H, CH2)] ppm.
(br., O−H), 3059, 2914 (C−H), 1666 (C=O), 1577 (C=C),
−1 1
1199 (C−O), 702 (C−Br) cm . H NMR (400 MHz, CDCl3)
13
C NMR (100 MHz, DMSO-d6) δ = 199.5, 197.5 (C=O),
3
3
δ = 7.97 (d, JH,H = 7.6 Hz, 2H, CHAr), 7.77 (d, JH,H = 7.6
Hz, 2H, CHAr), 7.51−7.56 (m, 3H, CHAr), 7.41−7.44 (m,
2H, CHAr), 7.19−7.33 (m, 5H, CHAr), 5.45 (m, 1H, CH−O),
138.8, 135.7, 135.5, 133.7, 130.5, 129.3, 129.2, 129.17, 69.1,
42.6 ppm. Anal. Calcd for C16H13ClO3 (288.73): C 66.56,
H 4.54; Found: C 66.49, H 4.51%.
Journal of the Korean Chemical Society

DABCO-Catalyzed Green Synthesis of 2-Hydroxy-1,4-diones via Direct Aldol Reaction of Arylglyoxals in Water
257
3
3.47 (dd, JH,H = 7.2, 17.2 Hz, 1H, CH2), 3.34−3.39 (dd,
4-(4-Bromophenyl)-2-hydroxy-1-phenylbutane-1,4-
dione (5b)
3
13
JH,H = 3.6, 17.2 Hz, 1H, CH2)] ppm. C NMR (100 MHz,
o
White solid, m.p. 145.8−149.6 C. FT-IR (KBr) ν = 3448
CDCl3) δ = 199.3, 196.3 (C=O), 140.6, 140.3, 134.8, 132.0,
130.2, 129.8, 129.3, 129.1, 70.3, 43.1 ppm. Anal. Calcd
for C16H12Cl2O3 (323.17): C 59.46, H 3.74; Found: C
59.40, H 3.74%.
(br., O−H), 3058, 2964 (C−H), 1676 (C=O), 1583 (C=C),
−1 1
1191 (C−O), 696 (C−Br) cm . H NMR (400 MHz, CDCl3)
3 3
δ = 8.01 (d, JH,H = 7.6 Hz, 2H, CHAr), 7.83 (d, JH,H = 8.4
3
Hz, 2H, CHAr), 7.61−7.67 (m, 3H, CHAr), 7.54 (t, JH,H
=
4-(4-Bromophenyl)-1-(4-chlorophenyl)-2-hydroxyb-
utane-1,4-dione (5f)
3
7.6 Hz, 2H, CHAr), 5.68 (m, 1H, CH−O), 4.04 (d, JH,H
=
13
o
White solid, m.p. 172−177 C. FT-IR (KBr) ν = 3450
6.0 Hz, 1H, OH), 3.33−3.44 (m, 2H, CH2) ppm. C NMR
(100 MHz, CDCl3) δ = 200.6, 196.3 (C=O), 135.4, 134.1,
133.5, 132.0, 129.9, 129.0, 128.9, 128.7, 70.1, 43.5 ppm.
Anal. Calcd for C16H13BrO3 (333.18): C 57.68, H 3.93;
Found: C 57.50, H 4.00%.
(O−H), 3080 (C−H), 1674 (C=O), 1581 (C=C), 1197 (C−
−1 1
O), 771 (C−Cl), 574 (C−Br) cm . H NMR (400 MHz,
3
CDCl3) δ = 7.98 (d, JH,H = 8.4 Hz, 2H, CHAr), 7.83 (d,
3
3
JH,H = 8.4 Hz, 2H, CHAr), 7.64 (d, JH,H = 8.4 Hz, 2H,
3
CHAr), 7.51 (d, JH,H = 8.4 Hz, 2H, CHAr), 5.59-5.61 (m,
2-Hydroxy-4-(4-nitrophenyl)-1-phenylbutane-1,4-
dione (5c)
3
1H, CH−O), 4.01 (d, JH,H = 6.4 Hz, 1H, OH), 3.33−3.47
o
Yellow solid, m.p. 128−132 C. FT-IR (KBr) ν = 3450
3
[2×dd: 3.41−3.47 (dd, JH,H = 6.8, 17.2 Hz, 1H, CH2),
3
13
(O−H), 3076 (C−H), 1670 (C=O), 1593 (C=C), 1521,
3.33−3.39 (dd, JH,H = 3.2, 17.2 Hz, 1H, CH2)] ppm. C
NMR (100 MHz, CDCl3) δ = 199.3, 196.6 (C=O), 140.6,
135.2, 132.1, 131.9, 130.2, 129.8, 129.3, 129.1, 70.3, 43.1
ppm. Anal. Calcd for C16H12BrClO3 (367.62): C 52.27, H
3.29; Found: C 52.30, H 3.22%.
-1 1
1315 (NO2), 1195 (C−O) cm . H NMR (400MHz, CDCl3)
3 3
δ = 8.34 (d, JH,H = 8.8 Hz, 2H, CHAr), 8.13 (d, JH,H = 8.8
3
Hz, 2H, CHAr), 8.02 (d, JH,H = 7.6 Hz, 2H, CHAr), 7.67 (t,
3
JH,H = 7.6 Hz, 1H, CHAr), 7.54−7.58 (m, 2H, CHAr), 5.68−
3
5.72 (m, 1H, CH−O), 4.05 (d, JH,H = 6.0 Hz, 1H, OH), 3.41−
1-(4-Chlorophenyl)-2-hydroxy-4-(thiophen-2-yl)butane-
1,4-dione (5g)
13
3.47 (m, 2H, CH2) ppm. C NMR (100 MHz, CDCl3) δ =
o
Cream solid, m.p. 131.6−135.1 C. FT-IR (KBr) ν = 3450
200.2, 195.9 (C=O), 150.6, 141.1, 134.3, 133.3, 129.4, 129.1,
128.7, 123.9, 70.0, 44.1 ppm. Anal. Calcd for C16H13NO5
(299.28): C 64.21, H 4.38, N 4.68; Found: C 64.18, H
4.31, N 4.55%.
(O−H), 3085, 2943 (C−H), 1695 (C=O), 1649 (C=C),
−1 1
1203 (C−O), 721 (C−Cl) cm . H NMR (400 MHz,
3
DMSO-d6) δ = 8.02−8.11 (m, 4H, CHAr), 7.63 (d, JH,H
=
3
8.4 Hz, 2H, CHAr), 7.26−7.28 (m, 1H, CHAr), 5.92 (d, JH,H
= 7.6 Hz, 1H, OH), 5.38−5.43 (m, 1H, CH−O), 3.35−3.51
1-(4-Chlorophenyl)-2-hydroxy-4-phenylbutane-1,4-
dione (5d)
o
White solid, m.p. 151−155 C. FT-IR (KBr) ν = 3440 (O−
13
(m, 2H, CH2) ppm. C NMR (100 MHz, CDCl3) δ = 199.2,
H), 3080 (C−H), 1679 (C=O), 1554 (C=C), 1190 (C−O),
190.1, 143.7, 140.5, 134.9, 133.0, 131.9, 130.3, 129.3, 128.3,
70.4, 43.9 ppm. Anal. Calcd for C14H11ClO3S (294.75): C
57.05, H 3.76; Found: C 56.60, H 3.49%.
1-(4-Bromophenyl)-2-hydroxy-4-phenylbutane-1,4-
dione (5h)
−1 1
750 (C−Cl) cm . H NMR (400 MHz, CDCl3) δ = 7.96−
3
8.00 (m, 4H, CHAr), 7.62 (t, JH,H = 7.6 Hz, 1H, CHAr),
7.48−7.52 (m, 4H, CHAr), 5.59−5.63 (m, 1H, CH−O), 4.02
3
(d, JH,H = 6.4 Hz, 1H, OH), 3.38−3.52 [2×dd: 3.46−3.52
3 3
(dd, JH,H = 6.8, 17.2 Hz, 1H, CH2), 3.38−3.44 (dd, JH,H
o
White solid, m.p. 154.5−157.0 C. FT-IR (KBr) ν = 3438
=
13
3.6, 17.2 Hz, 1H, CH2)] ppm. C NMR (100 MHz, CDCl3)
δ = 199.5, 197.5 (C=O), 140.4, 136.5, 133.8, 132.1, 130.3,
129.3, 128.8, 128.3, 70.4, 43.2 ppm. Anal. Calcd for
C16H13ClO3 (288.73): C 66.56, H 4.54; Found: C 66.50, H
4.50%.
(O−H), 3086 (C−H), 1676 (C=O), 1573 (C=C), 1190 (C−
−1 1
O), 654 (C−Br) cm . H NMR (400 MHz, DMSO-d6) δ =
3
7.95−8.04 (m, 4H, CHAr), 7.78 (d, JH,H = 8.4 Hz, 2H,
3
CHAr), 7.67 (t, JH,H = 7.6 Hz, 1H, CHAr), 7.53−7.57 (m, 2H,
3
CHAr), 5.89 (d, JH,H = 7.6 Hz, 1H, OH), 5.38−5.44 (m,
13
1H, CH−O), 3.31−3.62 (m, 2H, CH2) ppm. C NMR (100
1,4-Bis(4-chlorophenyl)-2-hydroxybutane-1,4-dione (5e)
o
White solid, m.p. 159−162 C. FT-IR (KBr) ν = 3427
MHz, DMSO-d6) δ = 198.9, 198.3 (C=O), 136.9, 134.6,
133.9, 132.2, 131.3, 129.2, 128.5, 127.7, 69.2, 42.5 ppm.
Anal. Calcd for C16H13BrO3 (333.18): C 57.68, H 3.93;
Found: C 57.66, H 3.93%.
(O−H), 3071 (C−H), 1673 (C=O), 1588 (C=C), 1200 (C−
−1 1
O), 745 (C−Cl) cm . H NMR (400 MHz, CDCl3) δ =
3 3
7.98 (d, JH,H = 8.8 Hz, 2H, CHAr), 7.91 (d, JH,H = 8.8 Hz,
3
2H, CHAr), 7.51 (d, JH,H = 8.8 Hz, 2H, CHAr), 7.47 (d,
1-(4-Bromophenyl)-4-(4-chlorophenyl)-2-hydrox-
ybutane-1,4-dione (5i)
3
JH,H = 8.4 Hz, 2H, CHAr), 5.57−5.61 (m, 1H, CH−O),
3
4.01 (d, JH,H = 6.4 Hz, 1H, OH), 3.34−3.47 [2×dd: 3.41−
o
Cream solid, m.p. 168−173 C. FT-IR (KBr) ν = 3440 (O−
2013, Vol. 57, No. 2

258
Mahnaz Saraei, Bagher Eftekhari-Sis, and Sakineh Mozaffarnia
H), 3074 (C−H), 1676 (C=O), 1558 (C=C), 1197 (C−O),
135.9, 134.6, 132.3, 132.2, 131.3, 130.6, 127.9, 127.8,
69.4, 42.5 ppm. Anal. Calcd for C14H11BrO4 (323.14): C
52.04, H 3.43; Found: C 52.20, H 3.40%.
−1 1
771 (C−Cl), 690 (C−Br) cm . H NMR (400 MHz, CDCl3)
3
δ = 7.89−7.92 (m, 4H, CHAr), 7.68 (d, JH,H = 7.6 Hz, 2H,
3
CHAr), 7.47 (d, JH,H = 8.4 Hz, 2H, CHAr), 5.57−5.59 (m,
1H, CH−O), 4.01 (s, br., 1H, OH), 3.34−3.47 [2×dd: 3.41−
Acknowledgments. This work was supported by the
research council of the PNU and UM. B. E. S. gratefully
acknowledges Mr. Biglari (IASBS) for taking NMR spectra.
And the publication cost of this paper was supported by the
Korean Chemical Society.
3
3.47 (dd, JH,H = 7.2, 17.2 Hz, 1H, CH2), 3.34−3.39 (dd,
3
13
JH,H = 3.6, 17.2 Hz, 1H, CH2)] ppm. C NMR (100 MHz,
CDCl3) δ = 199.6, 196.3 (C=O), 140.3, 134.8, 132.4, 132.3,
130.3, 129.8, 129.3, 129.1, 70.3, 43.1 ppm. Anal. Calcd
for C16H12BrClO3 (367.62): C 52.27, H 3.29; Found: C
52.60, H 3.41%.
REFERENCES
1,4-Bis(4-bromophenyl)-2-hydroxybutane-1,4-dione (5j)
o
White solid, m.p. 185−189 C. FT-IR (KBr) ν = 3441
1. (a) Anastas, P.; Williamson, T. Green Chemistry, Frontiers in
Benign Chemical Synthesis and Procedures; Oxford Science
Publications: New York, 1998. (b) Hayashi, T.; Yamasaki, K.
Chem. Rev. 2003, 103, 2829.
(O−H), 3081 (C−H), 1674 (C=O), 1575 (C=C), 1199 (C−
−1 1
O), 675 (C−Br) cm . H NMR (400 MHz, CDCl3) δ =
3 3
7.90 (d, JH,H = 8.4 Hz, 2H, CHAr), 7.83 (d, JH,H = 8.0 Hz,
2. (a) Grieco, P. A. Organic Synthesis in Water; Blackie
Academic and Professional: London, 1998. (b) Li, C.-J.
Chem. Rev. 2005, 105, 3095. (c) Li, C.-J.; Chan, T.-H.
Organic Reactions in Aqueous Media; Wiley: New York,
1997. (d) Zuo, H.; Li, Z.-B.; Zhao, B.-X.; Miao, J.-Y.;
Meng, L.-J.; Jang, K.; Ahn, C.; Lee, D.-H.; Shin, D.-S.
Bull. Korean Chem. Soc. 2011, 32, 2965. (e) Islam, M.;
Hossain, D.; Mondal, P.; Roy, A. S.; Mondal, S.; Mobarak,
M. Bull. Korean Chem. Soc. 2010, 31, 3765. (f) Dhokte,
A. O.; Khillare, S. L.; Lande, M. K.; Arbad, B. R. J.
Korean Chem. Soc. 2011, 55, 430.
3
2H, CHAr), 7.68 (d, JH,H = 8.4 Hz, 2H, CHAr), 7.64 (d,
3
JH,H = 8.4 Hz, 2H, CHAr), 5.57−5.59 (m, 1H, CH−O),
3
4.00 (d, JH,H = 6.0 Hz, 1H, OH), 3.39−3.47 [2×dd: 3.41−
3
3.47 (dd, JH,H = 6.8, 17.2 Hz, 1H, CH2), 3.39−3.42 (dd,
3
13
JH,H = 3.6, 17.2 Hz, 1H, CH2)] ppm. C NMR (100 MHz,
CDCl3) δ = 199.5, 196.5 (C=O), 135.2, 134.4, 132.3,
132.1, 130.3, 129.8, 129.3, 129.1, 70.3, 43.1 ppm. Anal.
Calcd for C16H12Br2O3 (412.07): C 46.64, H 2.94; Found:
C 46.54, H 2.89%.
1-(4-Bromophenyl)-2-hydroxy-4-(4-nitrophenyl)butane-
1,4-dione (5k)
3. (a) Marhwald, R. Modern Aldol Reactions; Weinheim
Wiley-VCH: 2004. (b) Trost, B. M. Science 1991, 254,
1471. (c) Trost, B. M. Angew. Chem., Int. Ed. 1995, 34,
259. (d) Li, J.-Z.; Cui, B.-C.; Wang, J. J.; Shim, Y. K.
Bull. Korean Chem. Soc. 2011, 32, 2465. (e) Basaif, S. A.;
Sobahi, T. R.; Khalil, A. K.; Hassan, M. A. Bull. Korean
Chem. Soc. 2005, 26, 1677. (f) Jeong, T. M.; Park, K. H.
J. Korean Chem. Soc. 1989, 33, 426.
o
Yellow solid, m.p. 146−150 C. FT-IR (KBr) ν = 3429
(br., O−H), 3097 (C−H), 1677 (C=O), 1581 (C=C), 1519,
−1 1
1328 (NO2), 1195 (C−O), 688 (C−Br) cm . H NMR (400
3
MHz, DMSO-d6) δ = 8.36 (d, JH,H = 8.8 Hz, 2H, CHAr),
3 3
8.22 (d, JH,H = 8.8 Hz, 2H, CHAr), 7.98 (d, JH,H = 8.4 Hz,
3
2H, CHAr), 7.78 (d, JH,H = 8.4 Hz, 2H, CHAr), 6.00 (d,
4. (a) Scheidt, K. A.; Bannister, T. D.; Tasaka, A.; Wendt,
M. D.; Savall, B. M.; Fegley, G. J.; Roush, W. R. J. Am.
Chem. Soc. 2002, 124, 6981. (b) White, J. D.; Blakemore,
P. R.; Green, N. J.; Hauser, E. B.; Holoboski, M. A.;
Keown, L. E.; Kolz, C. S. N.; Phillips, B. W. J. Org.
Chem. 2002, 67, 7750. (c) Gerber-Lemaire, S.; Vogel, P.
Eur. J. Org. Chem. 2003, 2959. (d) Casiraghi, G.; Zanardi,
F.; Appendino, G.; Rassu, G. Chem. Rev. 2000, 100, 1929.
5. (a) Nicolaou, K. C.; Vourloumis, D.; Wissinger, N.; Baran, P.
S. Angew. Chem., Int. Ed. 2000, 39, 44. (b) Evans, D. A.;
Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem.
Soc. 1995, 117, 3448. (c) Keck, G. E.; Wager, C. A.; Sell,
T.; Wager, T. T. J. Org. Chem. 1999, 64, 2172.
3
JH,H = 7.6 Hz, 1H, OH), 5.41−5.46 (m, 1H, CH−O),
3
3.44−3.69 [2×dd: 3.62−3.69 (dd, JH,H = 6.4, 17.2 Hz, 1H,
3
CH2), 3.44−3.49 (dd, JH,H = 6.0, 17.2 Hz, 1H, CH2)] ppm.
13
C NMR (100 MHz, DMSO-d6) δ = 199.2, 196.2 (C=O),
151.1, 140.9, 139.6, 132.4, 130.3, 129.5, 129.4, 124.0, 70.3,
43.6 ppm. Anal. Calcd for C16H12BrNO5 (378.17): C
50.82, H 3.20, N 3.70; Found: C 50.80, H 3.21, N 3.89%.
1-(4-Bromophenyl)-4-(furan-2-yl)-2-hydroxybutane-
1,4-dione (5l)
o
Cream solid, m.p. 168.0−173.0 C. FT-IR (KBr) ν = 3620
(O−H), 1679 (C−O), 1550 (C=C), 1198 (C=O), 675 (C−Br)
−1 1 3
cm . H NMR (400 MHz, DMSO-d6) δ = 7.96 (d, JH,H
6. (a) Stetter, H.; Kulhmann, H. Synthesis 1975, 379. (b)
Mussatto, M. C.; Savoia, D.; Trombini, C.; Umani-Ronchi,
A. J. Org. Chem. 1980, 45, 4002. (c) Wenkert, E.; Green-
berg, R. S.; Ragu, M. S. J. Org. Chem. 1985, 50, 4681. (d)
Takahashi, K.; Aihara, T.; Ogura, K. Chem. Lett. 1987, 2359.
(e) Curran, D. P. Tetrahedron 1994, 58, 1181. (f) Banik,
=
3
8.4 Hz, 2H, CHAr), 7.92 (d, JH,H = 8.4 Hz, 2H, CHAr),
3
7.75−7.79 (m, 3H, CHAr), 5.91 (d, JH,H = 7.6 Hz, 1H, OH),
5.37−5.42 (m, 1H, CH−O), 3.33−3.59 (m, 2H, CH2) ppm.
13
C NMR (100 MHz, DMSO-d6) δ = 198.8, 197.6 (C=O),
Journal of the Korean Chemical Society

DABCO-Catalyzed Green Synthesis of 2-Hydroxy-1,4-diones via Direct Aldol Reaction of Arylglyoxals in Water
259
B. K.; Banik, I.; Renteria, M.; Dasgupta, S. K. Tetrahe-
dron Lett. 2005, 46, 2643. (g) Ho, T.-L. Synth. Commun.
1974, 4, 265. (h) Ballini, R.; Petrini, M. Synth. Commun.
1989, 19, 575. (i) Yamashita, M.; Tashika, H.; Uchida, M.
Bull. Chem. Soc. Jpn. 1992, 65, 1257. (j) Bentley, P. H.
Chem. Soc. Rev. 1974, 29. (k) Mitra, A. The Synthesis of
Prostaglandins; Wiley: New York, 1977. (l) Bindra, J. S.;
Bindra, R. Prostaglandin Synthesis; Academic Press:
New York, 1977.
11. (a) Hassner, A.; Lokanatha Rai, K. M. In Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Per-
gamon: Oxford, 1991; Vol. 2, p 541. (b) Stetter, H.; Kuhl-
mann, H. Org. React. 1991, 40, 407. (c) Mattson, A. E.;
Bharadwaj, A. R.; Scheidt, K. A. J. Am. Chem. Soc. 2004,
126, 2314. (d) Johnson, J. S. Angew. Chem., Int. Ed. 2004, 43,
1326. (e) Myers, M. C.; Bharadwaj, A. R.; Milgram, B.
C.; Scheidt, K. A. J. Am. Chem. Soc. 2005, 127, 14675.
12. Calter, M. A.; Zhu, C. Org. Lett. 2002, 4, 205.
13. Enders, D.; Balensiefer, T. Acc. Chem. Res. 2004, 37, 534.
14. (a) Stetter, H.; Kuhlmann, H. Synthesis 1975, 379. (b)
Yadav, J. S.; Anuradha, K.; Reddy, B. V. S.; Eeshwaraiah,
B. Tetrahedron Lett. 2003, 44, 8959. (c) Amarnath, V.;
Anthony, D. C.; Amarnath, K.; Valentine, W. M.; Wet-
terau, L. A.; Graham, D. G. J. Org. Chem. 1991, 56, 6924.
(d) Kerr, M. S.; Read de Alaniz, J.; Rovis, T. J. Org. Chem.
2005, 70, 5725.
7. (a) Gribble, G. W. In Comprehensive Heterocyclic Chem-
istry; Katrizky, A. R., Rees, C. W., Scriven, E. F., Eds.;
Pergamon: Oxford, 1996; Vol. 2, p. 207. (b) Benassi, R.
In Comprehensive Heterocyclic Chemistry; Katrizky, A.
R., Rees, C. W., Scriven, E. F., Eds.; Pergamon: New York,
1996; Vol. 2, p. 259. (c) Hirano, K.; Biju, A. T.; Piel, I.;
Glorius, F. J. Am. Chem. Soc. 2009, 131, 14190. (d) Biju, A.
T.; Glorius, F. Angew. Chem., Int. Ed. 2010, 49, 9761. (e)
Mortensen, D. S.; Rodriguez, A. L.; Carlson, K. E.; Sun,
J.; Katzenellenbogen, B. S.; Katzenellenbogen, J. A. J.
Med. Chem. 2001, 44, 3838. (f) El-Haji, T.; Martin, J. C.;
Descotes, G. J. J. Heterocycl. Chem. 1983, 20, 233. (g)
Perrine, D. M.; Kagan, J.; Huang, D. B.; Zeng, K.; Theo,
B. K. J. Org. Chem. 1987, 52, 2213. (h) Bellina, F.; Rossi,
R. Tetrahedron 2006, 62, 7213. (i) Lipshutz, B. H. Chem.
Rev. 1986, 86, 795. (j) Rao, H. S. P.; Jothilingam, S. J.
Org. Chem. 2003, 68, 5392.
15. Smith, A. B., III; Adams, C. M. Acc. Chem. Res. 2004,
37, 365.
16. Eftekhari-Sis, B.; Zirak, M.; Akbari, A. Chem. Rev. 2013,
doi: 10.1021/cr300176g.
17. Tokuda, O.; Kano, T.; Gao, W.-G.; Ikemoto, T.; Maruoka,
K. Org. Lett. 2005, 7, 5103.
18. (a) Allen, C. F. H. Can. J. Res. 1931, 4, 264. (b) Allen,
C. F. H.; Van Allan, J. A. J. Org. Chem. 1951, 16, 716.
(c) Hara, N.; Nakamura, S.; Shibata, N.; Toru, T. Adv.
Synth. Catal. 2010, 352, 1621. (d) Samanta, S.; Zhao, C.-G.
Tetrahedron Lett. 2006, 47, 3383. (e) Langer, P.; Köhler,
V. Org. Lett. 2000, 2, 1597.
8. (a) Katritzky, A. R.; Zhang, G. F.; Jiang, J. L. J. Org. Chem.
1995, 60, 7605. (b) Lu, X. Y.; Ji, J. G.; Ma, D. W.; Shen,
W. J. Org. Chem. 1991, 56, 5774. (c) Yasuda, M.; Tsuji,
S.; Shigeyoshi, Y.; Baba, A. J. Am. Chem. Soc. 2002, 124,
7440. (d) Yuguchi, M.; Tokuda, M.; Orito, K. J. Org. Chem.
2004, 69, 908. (e) Xue, A. S.; Li, L.; Liu, Y.; Guo, Q. J.
Org. Chem. 2006, 71, 215. (f) Matsubara, R.; Doko, T.;
Uetake, R.; Kobayashi, S. Angew. Chem., Int. Ed. 2007,
46, 3047.
19. Zhao, J.; Zheng, K.; Yang, Y.; Shi, J.; Lin, L.; Liu, X.;
Feng, X. Synlett 2011, 903.
20. Riley, H. A.; Gray, A. R. Organic Syntheses, Wiley &
Sons: New York, 1943, collect; Vol. II, p. 509.
21. By permission of Allgood, T. Scientific Account Manager
CCDC; Macrae, C. F.; Edgington, P. R.; McCabe, P.; Pid-
cock, E.; Shields, G. P.; Taylor, R.; Towler, M.; van de
Streek, J. J. Appl. Cryst. 2006, 39, 453.
9. Seyferth, D.; Hui, R. C. J. Am. Chem. Soc. 1985, 107, 4551.
10. (a) Cooke, M. P., Jr.; Parlman, R. M. J. Am. Chem. Soc.
1977, 99, 5222. (b) Hegedus, L. S.; Perry, R. J. J. Org.
Chem. 1985, 50, 4955. (c) Hermanson, J. R.; Hershberger, J.
W.; Pinhas, A. R. Organometallics 1995, 14, 5426. (d)
Lipshutz, B. H.; Elworthy, T. R. Tetrahedron Lett. 1990,
31, 477.
22. Eftekhari-Sis, B.; Akbari, A.; Amirabedi, M. Chem. Hetero-
cycl. Comp. 2011, 46, 1330.
23. Harms, K. Private communication to the Cambridge Struc-
tural Database. deposition number CCDC 784184.
2013, Vol. 57, No. 2