Samarium(III) iodide promoted three-component coupling reactions of aldehydes, α-haloketones, and active methylene or methyl compounds

Article abstract of DOI:10.1081/SCC-120016312

In the presence of samarium(III) iodide, the reaction of aldehydes, α-haloketones with malononitrile, ethylcyanoacetate or nitromethane proceeded very efficiently and furnished moderate to high yields of adducts.

Full text of DOI:10.1081/SCC-120016312

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Samarium(III) Iodide Promoted Three-Component
Coupling Reactions of Aldehydes, α-Haloketones, and
Active Methylene or Methyl Compounds
Yongmin Ma a & Yongmin Zhang a b
a Department of Chemistry , Zhejiang University (Campus Xixi) , Hangzhou, P.R. China
b State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic
Chemistry , Chinese Academy of Sciences , Shanghai, P.R. China
Published online: 17 Aug 2006.
To cite this article: Yongmin Ma & Yongmin Zhang (2003) Samarium(III) Iodide Promoted Three-Component Coupling Reactions
of Aldehydes, α-Haloketones, and Active Methylene or Methyl Compounds, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 33:5, 711-715, DOI: 10.1081/SCC-120016312
To link to this article: http://dx.doi.org/10.1081/SCC-120016312
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 5, pp. 711–715, 2003
Samarium(III) Iodide Promoted
Three-Component Coupling Reactions of
Aldehydes, a-Haloketones, and
Active Methylene or Methyl Compounds
Yongmin Ma1 and Yongmin Zhang1,2,
*
1Department of Chemistry, Zhejiang University
(Campus Xixi), Hangzhou, P.R. China
2State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai, P.R. China
ABSTRACT
In the presence of samarium(III) iodide, the reaction of aldehydes,
a-haloketones with malononitrile, ethylcyanoacetate or nitro-
methane proceeded very efficiently and furnished moderate to high
yields of adducts.
Key Words: Samarium(III) iodide; Aldehydes; Alph-haloketones;
Active methylene compounds; Three-component coupling reaction.
*Correspondence: Yongmin Zhang, Department of Chemistry, Zhejiang
University (Campus Xixi), Hangzhou, 310028, P.R. China; Fax: þ86-571-
88807077; E-mail: yminzhang@mail.hz.zj.cn.
711
DOI: 10.1081/SCC-120016312
Copyright & 2003 by Marcel Dekker, Inc.
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712
Ma and Zhang
ArCHCH2COPh
j
SmI3
ArCHO þ PhCOCH2Br þ XCH2Y À!
XCHY
1
2
3
4
Scheme 1.
Table 1. Three-component coupling reactions promoted by SmI3.
Entry
Ar
XCH2Y
Yield (%)a
a
b
c
d
e
f
C6H5
CH2(CN)2
CH2(CN)2
CH2(CN)2
CH2(CN)2
NCCH2CO2Et
NCCH2CO2Et
NCCH2CO2Et
NCCH2CO2Et
CH3NO2
75
69
70
73
53
50
48
54
79
78
79
83
p-CH3C6H4
p-ClC6H4
p-CH3OC6H4
C6H5
p-CH3C6H4
p-ClC6H4
p-CH3OC6H4
C6H5
g
h
i
j
p-CH3C6H4
p-ClC6H4
p-CH3OC6H4
CH3NO2
CH3NO2
CH3NO2
k
l
aIsolated yield.
Herein, we wish to report our results on three-component coupling
reactions of aldehydes, a-haloketone, and active methylene or methyl
compounds promoted by SmI3 in one pot to formthe adducts (Sch. 1).
When aryl aldehydes (1) and a-haloketone (2) were treated with 2
equiv. SmI3 for about 2 h at room temperature, almost all of them were
consumed and the corresponding immediate products a,b-unsaturated
ketones were formed, then a solution of active methylene or methyl
compound (3) was added to the flask, the product 1,1-disubsituted-
2-aryl-3-benzoyl-propane (4) can be obtained in moderate to fine
yields. The results were summarized in Table 1.
FromTable 1 we can find that the reactions of equimolar benzalde-
hydes, a-haloketones with malononitrile or nitromethane in the presence
of two equivalent of SmI3 gave the adducts in good yields; But when
ethylcyanoacetate was used as nucleophilic reagent instead of malono-
nitrile or nitromethane, the yields were comparatively low. However,
the reactions of benzaldehydes, acetophone with active methylene

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Samarium(III) Iodide
713
compounds in the same conditions couldn’t give the corresponding
adducts. Besides, when the aliphatic aldehydes instead of the benzalde-
hydes, the corresponding products couldn’t be obtained either.
In summary, we have found that samarium triiodide promotes the
three-component coupling reactions of aldehydes, a-haloketones, and
active methylene or methyl compounds (for example: malononitrile,
ethylcyanoacetate, nitromethane) to form 1,1-disubstituted-2-aryl-3-
benzoyl-propanes in moderate to high yields. Further studies to develop
other new use of SmI3 are now in progress.
EXPERIMENTAL
Tetrahydrofuran was distilled from sodium-benzophenone immedi-
ately prior to use. All reactions were conducted under a nitrogen atmo-
sphere. Melting points were uncorrected. Infrared spectra were recorded
on a Perkin-Elmer 683 spectrometer in KBr with absorptions in cmÀ1
.
1H-NMR spectra were determined on a Bruker AC 80 spectrometer as
CDCl3 solutions. Chemical shifts were expressed in ppm downfield from
internal standard tetramethylsilane. Mass spectra were recorded on
HP5989B mass spectrometer. Elemental analyses were carried out on
an EA 1110 instrument.
General Procedure for the Preparation of
1,1-Disubstituted-2-aryl-3-benzoyl-propane (4)
To a mixture of aldehyde (1 mmol) and a-haloketones (1 mmol) in
anhydrous THF (3 mL) was added to a solution of SmI3 (2 mmol, in
20 mL THF). The mixture was stirred to room temperature for 2 h,
then a solution of active methylene compound (1 mmol) was added.
The mixture was refluxed for 20–24 h, then water was added and the
product was extracted with diethyl ether. The organic phase was
collected, dried (Na2SO4), and evaporated to afford the crude product.
The product was purified by preparative TLC on silica gel using cyclo-
hexane and ethyl acetate (6:1) as eluent.
3-Benzoyl-1,1-dicyano-2-phenyl-propane (4a): M.p. 122–125ꢀC, lit.,[1]
125–126ꢀC. ꢀmax (KBr)/cmÀ1: 2260, 1680. ꢁH (CDCl3): 3.60–3.68 (2H, d,
J ¼ 7.2 Hz, CH2), 3.85–4.18 (1H, m, CH), 4.60–4.66 (1H, d, J ¼ 4.8 Hz,
CH), 7.10–8.00 (10H, m, ArH).
3-Benzoyl-1,1-dicyano-2-(4-methylphenyl)-propane (4b): M.p. 126–128ꢀC.
ꢀmax (KBr)/cmÀ1: 2255, 1675. ꢁH (CDCl3): 2.28 (3H, s, CH3), 3.24–3.27

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714
Ma and Zhang
(2H, d, J ¼ 6.6 Hz, CH2), 3.44–3.65 (1H, m, CH), 4.40–4.55 (1H, d,
J ¼ 4.2 Hz, CH), 6.92–8.03 (9H, m, ArH). m/z: 306 (Mþ, 1.3), 105 (100).
Anal. calcd. for C19H16N2O: C, 79.14; H, 5.59; N, 9.72. Found: C, 78.75;
H, 5.78; N, 9.91.
3-Benzoyl-2-(4-chlorophenyl)-1,1-dicyano-propane (4c): M.p. 114–116ꢀC,
lit.,[1] 115–116ꢀC. ꢀmax (KBr)/cmÀ1: 2255, 1680. ꢁH (CDCl3): 3.55–3.64
(2H, d, J ¼ 7.2 Hz, CH2), 3.78–4.20 (1H, m, CH), 4.58–4.64 (1H, d,
J ¼ 4.8 Hz, CH), 7.10–8.13 (9H, m, ArH).
3-Benzoyl-2-(4-methoxyphenyl)-1,1-dicyano-propane(4d):M.p.117–119ꢀC,
lit.,[1] 117ꢀC. ꢀmax (KBr)/cmÀ1: 2255, 1675. ꢁH (CDCl3): 3.34–3.38 (2H, d,
J ¼ 7.2 Hz, CH2), 3.48–3.94 (4H, m, CH, OCH3), 4.47–4.54 (1H, d,
J ¼ 4.8 Hz, CH), 6.80–7.98 (9H, m, ArH).
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-phenyl-propane (4e): Oil. ꢀmax
(KBr)/cmÀ1: 2250, 1745, 1680. ꢁH (CDCl3): 0.93 (3H, t, J ¼ 6.4 Hz, CH3),
3.56–3.65 (2H, d, J ¼ 7.2 Hz, CH2), 3.86–4.15 (3H, m, CH, OCH2),
4.52–4.56 (1H, d, J ¼ 3.2 Hz, CH), 7.30–8.05 (10H, m, ArH). m/z: 321
(Mþ, 1.2), 105 (100).
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-(4-methylphenyl)-propane (4f ):
Oil. ꢀmax (KBr)/cmÀ1: 2250, 1745, 1685. ꢁH (CDCl3): 1.09 (3H, t,
J ¼ 7.2 Hz, CH3), 2.22 (3H, s, CH3), 3.40–3.54 (2H, d, J ¼ 7.5 Hz,
CH2), 3.72–4.24 (4H, m, 2CH, OCH2), 7.00–7.97 (9H, m, ArH). m/z:
335 (Mþ, 1.3), 105 (100).
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-(4-chlorophenyl)-propane (4g):
Oil. ꢀmax (KBr)/cmÀ1: 2250, 1740, 1685. ꢁH (CDCl3): 0.99 (3H, t,
J ¼ 7.2 Hz, CH3), 3.59–3.67 (2H, d, J ¼ 6.4 Hz, CH2), 3.86–4.24 (3H, m,
CH, OCH2), 4.63–4.67 (1H, d, J ¼ 3.2 Hz, CH), 7.21–7.90 (9H, m, ArH).
m/z: 355 (Mþ, 1.4), 105 (100).
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-(4-methoxyphenyl)-propane (4h):
Oil. ꢀmax (KBr)/cmÀ1: 2250, 1745, 1685. ꢁH (CDCl3): 1.04 (3H, t,
J ¼ 7.2 Hz, CH3), 3.37–3.55 (2H, d, J ¼ 7.5 Hz, CH2), 3.68–4.29 (7H, m,
2CH, OCH3, OCH2), 6.78–7.97 (9H, m, ArH). m/z: 351 (Mþ, 1.0), 105
(100).
4-Nitro-1,3-diphenyl-1-butanone (4i): M.p. 98–100ꢀC, lit.,[3,4] 100–
101ꢀC. ꢀmax (KBr)/cmÀ1: 1685, 1545, 1375. ꢁH (CDCl3): 3.40–3.48 (2H,
d, J ¼ 6.4 Hz, CH2), 4.00–4.34 (1H, m, CH), 4.66–4.77 (2H, d, J ¼ 8.8 Hz,
CH2), 7.14–7.90 (10H, m, ArH).
4-Nitro-1-phenyl-3-(4-methylphenyl)-1-butanone (4j): M.p. 84–86ꢀC.
ꢀmax (KBr)/cmÀ1: 1680, 1540, 1380. ꢁH (CDCl3): 2.30 (3H, s, CH3),
3.38–3.46 (2H, d, J ¼ 6.6 Hz, CH2), 4.01–4.71 (3H, m, CH, CH2),
7.14–7.92 (9H, m, ArH). m/z: 237 (M-46, 1.2), 236 (3.5), 105 (100).
Anal. calcd. for C17H17NO3: C, 72.07; H, 6.05; N, 4.94. Found: C,
71.81; H, 5.95; N, 5.16.

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Samarium(III) Iodide
715
4-Nitro-1-phenyl-3-(4-chlorophenyl)-1-butanone (4k): M.p. 110–111ꢀC.
ꢀmax (KBr)/cmÀ1: 1680, 1550, 1360. ꢁH (CDCl3): 3.44–3.52 (2H, d,
J ¼ 6.4 Hz, CH2), 4.08–4.37 (1H, m, CH), 4.68–4.79 (2H, d, J ¼ 8.8 Hz,
CH2), 7.14–8.01 (9H, m, ArH). m/z: 257 (M-46, 0.8), 256 (1.9), 105
(100). Anal. calcd. for C20H18ClNO3: C, 63.27; H, 4.65; N, 4.61. Found:
C, 63.10; H, 4.64; N, 4.63.
4-Nitro-1-phenyl-3-(4-methoxyphenyl)-1-butanone (4l): M.p. 64–66ꢀC,
lit.,[2] 66ꢀC. ꢀmax (KBr)/cmÀ1: 1680, 1540, 1380. ꢁH (CDCl3): 3.38–3.46
(2H, d, J ¼ 6.8 Hz, CH2), 3.78 (3H, s, CH3), 4.05–4.67 (3H, m, CH, CH2),
6.79–7.90 (9H, m, ArH).
ACKNOWLEDGMENTS
We are grateful to the National Natural Science Foundation of
China (Project No. 29872010) and the NSF of Zhejiang Province,
China for financial support.
REFERENCES
1. Krauze, A.; Bomika, Z.; Shestopalov, A.M.; Radinovskaya, L.A.;
Pelcers, J.; Duburs, G.; Sharanin, Yu.A.; Promonenkov, V.K. Khim
Geterotisikl. Soedin 1998, 3, 377.
2. Davey, W.; Tievey, D.J. J. Chem. Soc. 1958, 2276.
3. Gracia-Raso, A.; Garcia-Raso, J.; Campaner, B.; Mestres, R.;
Sinisterra, J.V. Synthesis 1982, 1037.
4. Pedro, V.; Jose, I.B.; Anton, V.F. Tetrahedron Lett. 1991, 32 (39),
5375.
Received in the Netherlands February 15, 2002

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