Ultrasound promoted synthesis of β-hydroxyesters by reformatsky reaction using indium metal

Article abstract of DOI:10.1081/SCC-100108228

Ultrasound promoted Reformatsky reaction by the reaction of aldehydes or ketone with ethyl bromoacetate in the presence of indium metal afforded β-hydroxyesters in good to excellent yields under mild conditions.

Full text of DOI:10.1081/SCC-100108228

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ULTRASOUND PROMOTED SYNTHESIS OF β-
HYDROXYESTERS BY REFORMATSKY REACTION USING
INDIUM METAL
Phil Ho Lee a , Keukchan Bang a , Kooyeon Lee a , Sun-young Sung a & Sukbok Chang b
a Department of Chemistry , Kangwon National University , Chunchon, 200-701, South
Korea
b Department of Chemistry , Ewha Womans University , Seoul, 120-750, South Korea
Published online: 09 Nov 2006.
To cite this article: Phil Ho Lee , Keukchan Bang , Kooyeon Lee , Sun-young Sung & Sukbok Chang (2001) ULTRASOUND
PROMOTED SYNTHESIS OF β-HYDROXYESTERS BY REFORMATSKY REACTION USING INDIUM METAL, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:24, 3781-3789,
DOI: 10.1081/SCC-100108228
To link to this article: http://dx.doi.org/10.1081/SCC-100108228
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SYNTHETIC COMMUNICATIONS, 31(24), 3781–3789 (2001)
ULTRASOUND PROMOTED SYNTHESIS
OF b-HYDROXYESTERS BY
REFORMATSKY REACTION USING
INDIUM METAL
Phil Ho Lee,1,* Keukchan Bang,1 Kooyeon Lee,1
Sun-young Sung,1 and Sukbok Chang2
1Department of Chemistry, Kangwon National
University, Chunchon 200-701, South Korea
2Department of Chemistry, Ewha Womans
University, Seoul 120-750, South Korea
This paper is dedicated to Professor In-Sup Han
on the occasion of his 65th birthday.
ABSTRACT
Ultrasound promoted Reformatsky reaction by the reaction
of aldehydes or ketone with ethyl bromoacetate in the pre-
sence of indium metal afforded b-hydroxyesters in good to
excellent yields under mild conditions.
The Reformatsky reaction, which is regarded as one of the most fun-
damental reactions in carbon–carbon bond formations, is the reaction
between a carbonyl compound with an a-haloester in the presence of zinc
*Corresponding author.
3781
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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LEE ET AL.
metal to furnish b-hydroxyesters.1 The products are one of the most imp-
ortant intermediates in organic synthesis.2 Recently, several modified
Reformatsky reactions using other metals have been described.3 Also, the
scope of the Reformatsky reaction has been extended with special tech-
niques for the activation of the metal (e.g. for removal of the oxide layer,
and the preparation of finely dispersed metal).4 The activation of zinc by
treatment with iodine or dibromomethane, or washing with dilute hydro-
chloric acid prior to use, is only moderately successful in the most known
procedures. Much more effective protocol is the use of special alloys – e.g.
zinc–copper couple, or the reduction of zinc halides using potassium (the
so-called Rieke procedure5) or potassium graphite.4 Although the applica-
tion of ultrasound has been reported for zinc metal, promoters such as
iodine and potassium iodide were needed sometimes to obtain the desired
products in good yields.6 Recently, we reported the indium mediated
organic reaction,7 and in this paper we describe the beneficial effects that
ultrasonic irradiation has on the indium mediated Reformatsky reaction.
To find optimum conditions for ultrasound assisted Reformatsky reac-
tion using indium, initially benzaldehyde (entry 4) was reacted with ethyl
bromoacetate in the presence of indium in various solvents. Of the several
solvents tested, THF gave the best results in terms of conversion and reac-
tion times. The reaction of benzaldehyde with ethyl bromoacetate in the
presence of indium in THF afforded ethyl 3-hydroxy-3-phenylpropanoate
(4) in 97% yield. Sonications were carried out at room temperature in a
Fisher Scientific ultrasonic cleaner bath, which delivered a 43 kHz wave,
with a fixed electrical power of 435 W. However, the yields were decreased
in other solvents under the identical conditions despite longer reaction
times. Ultrasound promoted reaction condition was superior to stirring
condition. In the absence of sonic waves, the reaction occurs much more
slowly (17 h) and the yield of the b-hydroxyester 4 is only 70%. Rate per
minute (rpm) for stirring conditions is ca. 900. Ethyl iodoacetate gave the
similar results to ethyl bromoacetate.
Table 1 summarizes the experimental results and illustrates the effi-
ciency and scope of the present method.8 In case of aliphatic aldehydes
(entries 1, 2 and 3), the reaction afforded the desired compounds 1, 2 and
3 in excellent yields. For the aromatic aldehydes, the presence of various
substituents, e.g., methyl (entry 5), chloro (entry 6), bromo (entry 7), mono-
methoxy (entry 8), or dimethoxy (entry 9) on the aromatic ring showed little
effects on the efficiency of the reactions. It should be mentioned that 2- or
3-hydroxybenzaldehyde (entries 10 and 11) that contains an acidic hydrogen
was reacted with the same efficiency to provide the desired compounds 10
and 11 in 93 and 92% yields, respectively. The protocol developed here was
also applied to reactions with ketone. For example, acetophenone (entry 13)

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3783
Table 1. Preparation of b-Hydroxyesters by In-mediated Reactions of Carbonyl
Compounds with Ethyl Bromoacetate

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LEE ET AL.
was reacted under the identical conditions to give the b-hydroxyester 13 in
90% yield. However, indium promoted reaction of acetophenone with ethyl
bromoacetate gave b-hydroxyester 13 in 40% yield without sonic waves.
The sonicated mixture of zinc, ethyl bromoacetate, and acetophenone
gave no addition product in the absence of iodine.6
In summary, ultrasound mediated Reformatsky reaction using indium
afforded b-hydroxyesters in high yields. There are several advantages of
the method such as (a) the organoindium compound is prepared and used
in situ; (b) it has a wide application for elongation of carbon chains; (c)
compared to the use of zinc and tin, the reaction with indium did not require
any promoter (iodine or potassium iodide); and (d) the organo-indium
intermediates do not react with themselves in normal conditions. The pres-
ent method complements the existing synthetic methods because of mild
reaction condition and advantages of indium metal with regard to easy
handling, high reactivity and selectivity, low toxicity, and operational sim-
plicity. Further studies are now in progress.
EXPERIMENTAL SECTION
Typical procedure for indium-mediated Reformatsky reaction: Ethyl
3-hydroxy-3-phenylpropanoate (4). To a solution of indium (indium
powder (99.99%) purchased from Aldrich Chem Co.; 58.0 mg, 0.5 mmol)
in THF (1.0 mL) was added ethyl bromoacetate (125.0 mg, 0.75 mmol), then
benzaldehyde (53.0 mg, 0.5 mmol) under nitrogen at room temperature.
After sonicating in a Fisher Scientific ultrasonic cleaner bath, which deli-
vered a 43 kHz wave, with a fixed electrical power of 435 W, for 2 h, the
reaction mixture was quenched with saturated aqueous NaHCO3 solution.
The aqueous layer was extracted with ether (3 ꢀ 25 mL) and the combined
organic layers were washed with water (20 mL), brine (20 mL), dried with
MgSO4, filtered and concentrated in vacuo. The residue was purified by silica
gel chromatography (hexane : EtOAc ¼ 5:1) leading to ethyl 3-hydroxy-3-
1
phenylpropanoate (94.0 mg, 97%). H NMR (200 MHz, CDCl3) d 7.4–7.25
(5H, m, Ph), 5.14 (1H, q, J ¼ 4.0 Hz, H-3), 4.19 (2H, q, J ¼ 7.20 Hz, H-2),
3.14 (1H, br s, OH), 2.83–2.64 (2H, m, OCH2), 1.26 (3H, J ¼ 7.00 Hz,
OCH2CH3); 13C NMR (50 MHz, CDCl3) d 172.64 (s, C¼O), 142.62 (s, Ph-1),
128.69 (s, Ph-2,6), 127.94 (s, Ph-3,5), 125.81 (s, Ph-4), 70.40 (s, C-OH), 61.02
(s, OCH2CH3), 43.41 (s, OCOCH2), 14.23 (s, OCH2CH3); IR (film) 3460,
2980, 1720, 1490, 1450, 1395, 1370, 1295, 1260 cmÀ1; HRMS(CI) calcd for
C11H15O3 [M þ H]þ 195.1022, found 195.1028.
Ethyl 3-hydroxyhexanoate (1). 1H NMR (400 MHz, CDCl3) d 4.17
(2H, q, J ¼ 7.15 Hz, OCH2CH3), 4.02 (1H, m, H-3), 3.01 (1H, d, J ¼ 3.69 Hz,

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3785
OH), 2.49 (1H, dd, J ¼ 3.32, 3.16 Hz, H-2), 2.39 (1H, dd, J ¼ 8.93, 8.93 Hz,
H-2), 1.25–1.53 (4H, m, H-4,5), 1.27 (3H, t, J ¼ 7.20 Hz, OCH2CH3), 0.93
(3H, t, J ¼ 6.99 Hz, H-6); 13C NMR (100 MHz, CDCl3) d 173.13 (s, C¼O),
67.77 (s, C-OH), 60.67 (s, OCH2CH3), 41.38 (s, OCOCH2), 38.68 (s,
CH2CH2CH3), 18.69 (s, CH2CH2CH3), 14.19 (s, CH2CH2CH3), 13.97 (s,
OCH2CH3); IR (film) 3480, 3050, 2960, 1720, 1260 cmÀ1; HRMS(CI)
calcd for C8H17O3 [M þ H]þ 161.1179, found 161.1170.
1
Ethyl 3-hydroxy-4-methylpentanoate (2). H NMR (400 MHz, CDCl3)
d 4.17 (2H, q, J ¼ 7.14 Hz, OCH2), 3.78 (1H, m, H-3), 3.05 (1H, br s, OH),
2.50 (1H, dd, J ¼ 2.92, 2.92 Hz, H-2), 2.40 (1H, dd, J ¼ 9.53, 9.53 Hz, H-2),
1.72 (1H, m, H-4), 1.27 (3H, t, J ¼ 7.15 Hz, OCH2CH3), 0.94 (6H, q,
J ¼ 5.99 Hz, CH(CH3)2); 13C NMR (100 MHz, CDCl3) d 173.86 (s, C¼O),
73.09 (s, C-OH), 61.05 (s, OCH2CH3), 38.84 (s, OCOCH2), 33.52 (s,
CH(Me)2), 18.70 (s, CH(Me)2), 18.10 (s, CH(Me)2), 14.52 (s, OCH2CH3);
IR (film) 3440, 2975, 1720, 1470, 1370, 1320, 1270 cmÀ1; HRMS(CI) calcd
for C8H17O3 [M þ H]þ 161.1179, found 161.1185.
Ethyl 3-cyclohexyl-3-hydroxypropanoate (3). 1H NMR (400 MHz,
CDCl3) d 4.17 (2H, q, OCH2CH3), 3.79–3.75 (1H, m, H-3), 2.84 (1H, br s,
OH), 2.51 (1H, dd, J ¼ 2.80, 2.86 Hz, H-2), 2.41 (1H, dd, J ¼ 9.50, 9.49 Hz,
H-2), 1.86 (1H, d, J ¼ 12.65 Hz, H-4), 1.76 (2H, m, H-5), 1.66 (2H, d, J ¼
12.30 Hz, H-9), 1.41–1.11 (9H, m, H-6,7,8); 13C NMR (100 MHz, CDCl3) d
174.60 (s, C¼O), 73.17 (s, C-OH), 61.69 (s, OCH2CH3), 44.07 (s, OCOCH2),
39.59 (s, CHCH2CH2CH2CH2CH2), 29.80 (s, CHCH2CH2CH2CH2CH2),
29.27 (s, CHCH2CH2CH2CH2CH2), 27.44 (s, CHCH2CH2CH2CH2CH2),
27.18 (s, CHCH2CH2CH2CH2CH2), 27.06 (s, CHCH2CH2CH2CH2CH2),
15.20 (s, OCH2CH3); IR (film) 3500, 3050, 2980, 2920, 2840, 1720, 1450, 1410,
1370, 1260 cmÀ1; HRMS(CI) calcd for C 11H21O3 [M þ H]þ 201.1492, found
201.1480.
Ethyl3-hydroxy-3-( p-methylphenyl)propanoate(5).1H NMR(400 MHz,
CDCl3) d 7.25 (2H, d, J ¼ 8.02 Hz, Ph-2,6), 7.14 (2H, d, J ¼ 7.95 Hz, Ph-3,5),
5.08 (1H, q, J ¼ 4.18 Hz, H-3), 4.16 (2H, q, J ¼ 7.13 Hz, s, OCH2CH3), 3.1
(1H, br s, OH), 2.77–2.57 (2H, m, H-2), 2.33 (3H, s, 4-Me-Ph), 1.25 (3H, t,
J ¼ 7.14 Hz, s, OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.80 (s, C¼O),
140.04 (s, Ph-1), 137.84 (s, Ph-4), 129.58 (s, Ph-2,6), 126.02 (s, Ph-3,6), 70.57
(s, C-OH), 61.21 (s, OCH2CH3), 43.76 (s, OCOCH2), 21.49 (s, 4-Me-Ph),
14.54 (s, OCH2CH3); IR (film) 3410, 2960, 2900, 1715, 1510, 1440, 1390, 1365,
1290, 1260 cmÀ1; HRMS(CI) calcd for C 12H17O3 [M þ H]þ 209.1179, found
209.1165.
Ethyl 3-( p-chlorophenyl)-3-hydroxypropanoate (6). 1H NMR (400 MHz,
CDCl3) d 7.31 (4H, s, Ph), 5.09 (1H, q, J ¼ 4.25 Hz, H-3), 4.17 (2H,
q, J ¼ 7.12 Hz, s, OCH2CH3), 3.22 (1H, br s, OH), 2.68 (2H, m,
OCOCH2), 1.25 (3H, t, J ¼ 7.10 Hz, s, OCH2CH3); 13C NMR (100 MHz,

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LEE ET AL.
CDCl3) d 172.24 (s, C¼O), 141.03 (s, Ph-4), 133.45 (s, Ph-3,5), 128.67 (s, Ph-
1), 127.09 (s, Ph-2,6), 69.62 (s, C-OH), 61.00 (s, OCH2CH3), 43.20 (s,
OCOCH2), 14.13 (s, OCH2CH3); IR (film) 3400, 2930, 2860, 1695, 1470,
1375, 1350, 1280, 1260, 1240 cmÀ1; HRMS(CI) calcd for C 11H14Cl1O3
[M þ H]þ 229.0633, found 229.0641.
Ethyl3-(m-bromophenyl)-3-hydroxypropanoate(7).1H NMR(400 MHz,
CDCl3) d 7.55 (1H, t, J ¼ 1.62 Hz, Ph-2), 7.42–7.40 (1H, m, Ph-4), 7.30–7.19
(2H, m, Ph-5,6), 5.08 (1H, m, H-3), 4.18 (2H, q, J ¼ 7.14 Hz, OCH2CH3),
3.41 (1H, d, J ¼ 3.55 Hz, OH), 2.71 (2H, d, J ¼ 6.84 Hz, OCOCH2), 1.26
(3H, t, J ¼ 7.17 Hz, OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.23 (s,
C¼O), 144.78 (s, Ph-3), 130.84 (s, Ph-4), 130.12 (s, Ph-2), 128.87 (s, Ph-1),
124.28 (s, Ph-5), 122.67 (s, Ph-6), 69.59 (s, C-OH), 61.04 (s, OCH2CH3),
43.14 (s, OCOCH2), 14.14 (s, OCH2CH3); IR (film) 3500, 3050, 2980, 1720,
1420, 1260 cmÀ1; HRMS(CI) calcd for C 11H14Br1O3 [M þ H]þ 273.0128,
found 273.0120.
Ethyl 3-hydroxy-3-( p-methoxyphenyl)propanoate (8). 1H NMR
(400 MHz, CDCl3) d 7.30 (2H, d, J ¼ 8.09 Hz, Ph-3,5), 6.89 (2H, d, J ¼
8.49 Hz, Ph-2,6), 5.08 (1H, t, J ¼ 4.53 Hz, H-3), 4.18 (2H, q, J ¼ 7.14 Hz,
OCH2CH3), 3.79 (3H, s, OCH3), 3.20 (1H, br s, OH), 2.78–2.64 (2H, m,
H-2), 1.25 (3H, t, J ¼ 7.38 Hz, OCH2CH3); 13C NMR (100 MHz, CDCl3) d
172.44 (s, C¼O), 159.20 (s, Ph-4), 134.73 (s, Ph-1), 126.97 (s, Ph-2,6), 113.91
(s, Ph-3,5), 69.97 (s, C-OH), 60.83 (s, OCH2CH3), 55.29 (s, OCH3), 43.33 (s,
OCOCH2), 14.16 (s, OCH2CH3); IR (film) 3450, 2970, 2830, 1715, 1600,
1500, 1460, 1365, 1295, 1240 cmÀ1; HRMS(CI) calcd for C 12H17O4
[M þ H]þ 255.1128, found 255.1120.
Ethyl 3-hydroxy-3-(2,5-dimethoxyphenyl)propanoate (9). 1H NMR
(400 MHz, CDCl3) d 7.19 (1H, t, J ¼ 8.34 Hz, Ph-4), 6.56 (2H, d, J ¼
8.41 Hz, Ph-3,5), 5.66 (1H, dd, J ¼ 4.21, 4.31 Hz, H-3), 4.16 (2H, q,
J ¼ 7.14 Hz, OCH2CH3), 3.84 (6H, s, O(Me)2), 3.55 (1H, br s, OH), 2.99
(1H, dd, J ¼ 9.87, 9.91 Hz, H-2), 2.65 (1H, dd, J ¼ 4.25, 4.36 Hz, H-2), 1.26
(3H, t, J ¼ 7.1 Hz, OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.01
(s, C¼O), 158.07 (s, Ph-2,6), 129.30 (s, Ph-1), 118.40 (s, Ph-3,5), 104.59 (s,
Ph-4), 64.94 (s, C-OH), 60.79 (s, OCH2CH3), 56.10 (s, O(Me)2), 42.74
(s, OCOCH2), 14.60 (s, OCH2CH3); IR (film) 33525, 2960, 2920, 2820,
1720, 1580, 1460, 1365, 1260 cmÀ1; HRMS(CI) calcd for C 13H19O5 [M þ H]þ
255.1234, found 255.1225.
Ethyl 3-hydroxy-3-(o-hydroxyphenyl)propanoate (10). 1H NMR
(400 MHz, CDCl3) d 7.18 (1H, m, Ph-3), 6.98 (1H, dd, J ¼ 1.43, 1.43 Hz,
Ph-6), 6.88–6.81 (2H, m, Ph-4,5), 5.27 (1H, dd, J ¼ 3.06, 3.06 Hz, H-3),
4.21 (2H, q, J ¼ 7.14 Hz, OCH2CH3), 2.95 (1H, dd, J ¼ 10.27, 10.25 Hz,
H-2), 2.72 (1H, dd, J ¼ 3.16, 3.11 Hz, H-2), 1.28 (3H, t, J ¼ 7.15 Hz,
OCH2CH3); 13C NMR (100 MHz, CDCl3) d 173.08 (s, C¼O), 155.66 (s,

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3787
Ph-2), 129.32 (s, Ph-1), 126.66 (s, Ph-3), 125.31 (s, Ph-6), 119.97 (s, Ph-4),
117.48 (s, Ph-5), 71.48 (s, C-OH), 61.28 (s, OCH2CH3), 40.95 (s, OCOCH2),
14.11 (s, OCH2CH3); IR (film) 3370, 2980, 1700, 1610, 1490, 1450, 1370,
1350, 1220 cmÀ1; HRMS(CI) calcd for C 11H15O4 [M þ H]þ 211.0972, found
211.0985.
Ethyl 3-hydroxy-3-(m-hydroxyphenyl)propanoate (11). 1H NMR
(400 MHz, CDCl3) d 7.15 (1H, t, J ¼ 7.8 Hz, Ph-2), 6.83 (1H, d, J ¼
7.08 Hz, Ph-4,6), 6.73 (2H, m, Ph-5), 5.05 (3H, q, J ¼ 4.32 Hz, H-3,
OH), 4.14 (2H, q, J ¼ 7.13 Hz, OCH2CH3), 2.72 (1H, dd, J ¼ 9.02, 9.02 Hz,
H-2), 2.65 (1H, dd, J ¼ 3.95, 3.94 Hz, H-2), 1.23 (3H, t, J ¼ 7.13 Hz,
OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.64 (s, C¼O), 156.18 (s,
Ph-3), 143.96 (s, Ph-2), 129.81 (s, Ph-1), 117.74 (s, Ph-4), 115.10 (s, Ph-6),
112.77 (s, Ph-5), 70.38 (s, C-OH), 61.15 (s, OCH2CH3), 43.18 (s, OCOCH2),
14.07 (s, OCH2CH3); IR (film) 3380, 3050, 2980, 1720, 1600, 1450, 1420,
1250 cmÀ1; HRMS(CI) calcd for C 11H15O4 [M þ H]þ 211.0972, found
211.0970.
Ethyl 3-hydroxy-3-(2-thienyl)propanoate (12). 1H NMR (400 MHz,
CDCl3) d 7.26–7.23 (1H, m, S-CH), 6.96–6.94 (2H, m, SCH¼CH-CH),
5.36 (1H, m, H-3), 4.58 (2H, q, J ¼ 7.14 Hz, OCH2CH3), 3.55 (1H, d,
J ¼ 4.27 Hz, OH), 2.90–2.79 (1H, m, H-2), 1.26 (3H, t, J ¼ 7.2 Hz,
OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.32 (s, C¼O), 146.78
(s, thienyl-2), 127.1 (s, thienyl-5), 125.24 (s, thienyl-3), 124.03 (s, thienyl-
4), 66.95 (s, C-OH), 61.39 (s, OCH2CH3), 43.61 (s, OCOCH2), 14.53 (s,
OCH2CH3); HRMS(CI) calcd for C H13O3S1 [M þ H]þ 201.0587, found
9
201.0581.
Ethyl 3-hydroxy-3-phenylbutanoate (13). 1H NMR (400 MHz,
CDCl3) d 7.43 (2H, m, Ph-2,6), 7.33 (2H, m, Ph-3,5), 7.25–7.21 (1H, m,
Ph-4), 4.39 (1H, s, OH), 4.05 (2H, q, J ¼ 7.13 Hz, OCH2CH3), 2.88 (2H,
dd, J ¼ 15.8, 15.9 Hz, H-2), 1.54 (3H, s, CCH3), 1.12 (3H, t, J ¼ 7.2 Hz,
OCH2CH3); 13C NMR (100 MHz, CDCl3) d 172.72 (s, C¼O), 146.83 (s,
Ph-1), 128.23 (s, Ph-2,6), 126.84 (s, Ph-3,5), 124.45 (s, Ph-4), 72.74 (s,
C-OH), 60.73 (s, OCH2CH3), 46.41 (s, OCOCH2), 30.66 (s, CCH3), 13.98
(s, OCH2CH3); IR (film) 3460, 3020, 2960, 2900, 1690, 1480, 1430, 1360,
1320, 1240 cmÀ1; HRMS(CI) calcd for C 12H17O3 [M þ H]þ 209.1179, found
209.1173.
ACKNOWLEDGMENTS
This work was supported by Korea Research Foundation Grant
(KRF-99-005-D00048). The gas chromatograms were provided by GC faci-

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LEE ET AL.
lity, supported by Research Center for Advanced Mineral Aggregate
Composite Products.
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8. All new compounds have satisfactory analytical data including 1H,
13C-NMR, MS, and IR spectra. The NMR data were obtained from
central instrument facilities in Kangwon National University.
Received in the UK September 20, 2000

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