Michael additions of active methylene compounds to chalcones promoted by samarium(III) iodide

Article abstract of DOI:10.1081/SCC-120002689

Promoted by SmI₃, α,β-unsaturated ketones reacted with malononitrile, ethylcyanoacetate, diethylmalonate, β-ketoester or nitromethane to give the 1,4-adducts in moderate to good yields.

Full text of DOI:10.1081/SCC-120002689

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MICHAEL ADDITIONS OF ACTIVE METHYLENE
COMPOUNDS TO CHALCONES PROMOTED BY
SAMARIUM(III) IODIDE
Yongmin Ma a & Yongmin Zhang a b
a Department of Chemistry , Zhejiang University , Xixi Campus, Hangzhou, 310028, P.R.
China
b Laboratory of Organometallic Chemistry , Chinese Academy of Sciences , Shanghai,
200032, P.R. China
Published online: 16 Aug 2006.
To cite this article: Yongmin Ma & Yongmin Zhang (2002) MICHAEL ADDITIONS OF ACTIVE METHYLENE COMPOUNDS
TO CHALCONES PROMOTED BY SAMARIUM(III) IODIDE, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:6, 819-823, DOI: 10.1081/SCC-120002689
To link to this article: http://dx.doi.org/10.1081/SCC-120002689
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SYNTHETIC COMMUNICATIONS, 32(6), 819–823 (2002)
MICHAEL ADDITIONS OF ACTIVE
METHYLENE COMPOUNDS TO
CHALCONES PROMOTED BY
SAMARIUM(III) IODIDE
Yongmin Ma1 and Yongmin Zhang1,2,
*
1Department of Chemistry, Zhejiang University (Xixi
Campus), Hangzhou, 310028, P.R. China
2Laboratory of Organometallic Chemistry, Chinese
Academy of Sciences, Shanghai, 200032, P.R. China
ABSTRACT
Promoted by SmI3, a,b-unsaturated ketones reacted with
malononitrile, ethylcyanoacetate, diethylmalonate, b-keto-
ester or nitromethane to give the 1,4-adducts in moderate to
good yields.
In the last decades the application of lanthanoid compounds in
organic synthesis has been of great interest.1 Recently carbon–carbon
bond formation reactions mediated by trivalent lanthanoid have rapidly
increased. For example, lanthanoid trichlorides were used in combination
with NaBH4,2 LiAlH4,3 or Grignard reagent4 for selective reduction or
alkylation of carbonyl compounds; and CeI3 or CeI3/NaI was used in
the carbon–carbon bond formation between a-haloketones and aldehydes.5
*Corresponding author.
819
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

820
MA AND ZHANG
We reported that, promoted by SmI3, a-haloketones can react with alde-
hydes to give a,b-unsaturated ketones.6 We also reported that, mediated by
SmI3, b-diketones or b-ketoesters can condense with aldehydes to form
benzylidene-substituted b-diketones or b-ketoesters in good yield.7
The Michael reaction is one of the most useful methods for forming
carbon–carbon bond and has wide synthetic applications. The reaction
is usually carried out in the presence of a strong base (such as barium
hydroxide8a) or weak base (such as piperidine8b), but in these reaction
conditions, some side reactions will occur. Certainly many other methods
have been reported in fitting with this important reaction.9 Here, we wish
to report that, mediated by SmI3, active methylene compounds can
condense with chalcones to form 1,4-adducts in moderate to good yields
(Scheme 1).
Scheme 1.
The results were summarized in Table 1. We found that when, malono-
nitrile, b-ketoester, diethylmalonate or nitromethane reacted with chal-
cones, usually the products were obtained in high yields, but when
ethylcyanoacetate was ued as nucleophilic reagent, the yields were compara-
tively low. Unlike traditional base-promoted reactions, the reaction above
mentioned was performed in neutral, mild conditions and some side reac-
tions, which occurred in basic conditions, could be avoided.
EXPERIMENTAL
Tetrahydrofuran was distilled from sodium-benzophenone immedi-
ately prior to use. All reactions were conducted under a nitrogen atmos-
phere. Melting points were uncorrected. Infrared spectra were recorded on
a Perkin-Elmer 683 spectrometer in KBr with absorptions in cmꢀ1
1H-NMR spectra were determined on a Bruker AC 80spectrometer as
.
CDCl3 solutions. Chemical shifts were expressed in ppm downfield from
internal standard tetramethylsilane. Mass spectra were recorded on

MICHAEL ADDITIONS
821
Table 1. Michael Additions of Active Methylene Compounds with Chalcones
Induced by SmI3
Entry
Ar
C6H5
p-ClC6H4
C6H5
p-ClC6H4
C6H5
p-ClC6H4
C6H5
XCH2Y
NCCH2CN
NCCH2CN
NCCH2COOC2H5
NCCH2COOC2H5
CH3COCH2COOC2H5
CH3COCH2COOC2H5
C2H5OOCCH2COOC2H5
C2H5OOCCH2COOC2H5
CH3NO2
Yields (%)*
3a
3b
3c
3d
3e
3f
3g
3h
3i
86
80
67
64
88
87
88
83
90
81
p-ClC6H4
C6H5
p-ClC6H4
3j
CH3NO2
*Isolated yield.
HP5989B Mass spectrometer. Elemental analyses were carried out on an EA
1110instrument.
General procedure: Under anhydrous conditions, a mixture of
powdered samarium (0.30 g, 2 mmol) and iodine (0.75 g, 3 mmol) in
freshly distilled dry THF (20ml) was stirred at room temperature under
a N2 atmosphere. After Samarium disappeared (ca. 0.5 h), a solution
of chalcones 1 (2 mmol) and active methylene compounds 2 (2 mmol) in
anhydrous THF (3 ml) was added. The mixture was stirred for 20–24 h
at 65ꢁC. The reaction mixture became dark red and homogeneous.
Then the reaction mixture was quenched with 0.1 N HCl (5 ml) and
extracted with diethyl ether (3 ꢂ 15 ml). The combined extracts were
washed with a saturated solution of Na2S2O3 (15 ml) and a saturated
solution of NaCl (15 ml) then dried over anhydrous Na2SO4. After evapor-
ating the solvent under reduced pressure, the crude product was purified
by preparative TLC on silica gel using ethyl acetate-cyclohexane (1 : 6)
as eluent.
3-Benzoyl-1,1-dicyano-2-phenyl-propane (3a). M.p. 122–125ꢁC (lit.,10
125–126ꢁC). nmax (cmꢀ1): 2260(CN), 1680(CO). dH (ppm) 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-2-(40-chlorophenyl)-1,1-dicyano-propane
(3b).
M.p.
114–116ꢁC (lit.,10 115–116ꢁC). nmax (cmꢀ1): 2255 (CN), 1680(CO). dH
(ppm) 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).

822
MA AND ZHANG
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-phenyl-propane (3c). Oil. nmax
(cmꢀ1): 2250(CN), 1745 (COOC H5), 1680(CO). dH (ppm) 0.93 (3H, t,
2
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), 248 (26.8), 209 (16.4), 119 (11.3), 105 (100),
77 (31.2).
3-Benzoyl-1-cyano-1-ethoxycarbonyl-2-(40-chlorophenyl)-propane (3d).
Oil. nmax (cmꢀ1): 2250(CN), 1740(COOC 2H5), 1685 (CO). dH (ppm)
0.99 (3H, t, J ¼ 6.4 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 (Mꢀ, 1.4), 282 (22.9), 243 (16.4), 119
(13.8), 105 (100), 77 (40.4).
3-Benzoyl-1-acetyl-1-ethoxycarbonyl-2-phenyl-propane
(3e).
M.p.
120–122ꢁC (lit.,8 120–121ꢁC). nmax (cmꢀ1): 1745 (COOC2H5), 1710
(COCH3), 1680(COPh). dH (ppm) 0.95 (3H, t, J ¼ 6.4 Hz, CH3), 2.16
(3H, s, CH3), 3.48–3.57 (2H, d, J ¼ 7.2 Hz, CH2), 3.80–4.28 (4H, m, 2CH,
OCH2), 7.10–7.84 (10H, m, ArH).
3-Benzoyl-1-acetyl-1-ethoxycarbonyl-2-(40-chlorophenyl)-propane (3f).
M.p. 109–111ꢁC (lit.,8 110–111ꢁC). nmax (cmꢀ1): 1740(COOC H5), 1710
2
(COCH3). 1680, (COPh). dH (ppm) 1.00 (3H, t, J ¼ 6.4 Hz, CH3), 2.30
(3H, s, CH3), 3.45–3.55 (2H, d, J ¼ 8.0Hz, CH 2), 3.76–4.23 (4H, m, 2CH,
OCH2), 7.19–7.79 (9H, m, ArH).
3-Benzoyl-1,1-diethoxycarbonyl-2-phenyl-propane (3g). M.p. 63–65ꢁC
(lit.,8 65–67ꢁC). nmax (cmꢀ1): 1740(COOC H5), 1680(COPh). dH (ppm)
2
0.90 (3H, t, J ¼ 7.2 Hz, CH3), 3.38–3.47 (2H, d, J ¼ 7.2 Hz, CH2),
3.95–4.19 (5H, m, CH, 2OCH2), 4.40–4.43 (1H, d, J ¼ 2.4 Hz, CH),
7.14–7.94 (10H, m, ArH).
3-Benzoyl-1,1-diethoxycarbonyl-2-(40-chlorophenyl)-propane (3h). M.p.
93–95ꢁC (lit.,8 96–98ꢁC). nmax (cmꢀ1): 1740(COOC H5), 1680(COPh). dH
2
(ppm) 0.98 (3H, t, J ¼ 7.2 Hz, CH3), 3.36–3.46 (2H, d, J ¼ 8.0Hz, CH 2),
4.00–4.21 (5H, m, CH, 2OCH2), 4.42–4.45 (1H, d, J ¼ 2.4 Hz, CH),
7.14–8.13 (9H, m, ArH).
4-Nitro-1,3-diphenyl-1-butanone (3i). M.p. 98–100ꢁC (lit.,8 100–101ꢁC).
nmax (cmꢀ1): 1685 (COPh), 1545 (NO2), 1375 (NO2). dH (ppm) 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-(40-chlorophenyl)-1-butanone (3j). M.p. 110–111ꢁC.
nmax (cmꢀ1): 1680(COPh), 1550(NO 2), 1360(NO ). dH (ppm) 3.44–3.52
2
(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), 77 (26.7). Anal. Calcd for C20H18ClNO3: C, 63.27; H, 4.65; N,
4.61. Found: C, 63.10; H, 4.64; N, 4.63.

MICHAEL ADDITIONS
823
ACKNOWLEDGMENT
We are grateful to the National Natural Science Foundation of
China (Project No. 29872010) and the NSF of Zhejiang Province, China
for financial support.
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Received in the UK November 17, 2000