Samarium diiodide mediated reductive coupling of 2-nitro-1,3-diphenyl-2-propen-1-one: Synthesis of quinolines

Article abstract of DOI:10.1081/SCC-120014974

The intramolecular reductive cyclization of 2-nitro-1,3-diphenyl-2-propen-1-ones (1) induced by SmI₂ was investigated and 2-arylquinolines (2) were obtained in moderate to good yields at room temperature under neutral conditions.

Full text of DOI:10.1081/SCC-120014974

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SAMARIUM DIIODIDE MEDIATED REDUCTIVE COUPLING
OF 2-NITRO-1,3-DIPHENYL-2-PROPEN- 1-ONE:
SYNTHESIS OF QUINOLINES
Xiaoxia Wang a & Yongmin Zhang b
a Department of Chemistry , Zhejiang University (Campus Xixi) , Hangzhou, 310028, P.R.
China
b State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic
Chemistry , Chinese Academy of Sciences , Shanghai, 200032, P.R. China
Published online: 16 Aug 2006.
To cite this article: Xiaoxia Wang & Yongmin Zhang (2002) SAMARIUM DIIODIDE MEDIATED REDUCTIVE COUPLING OF 2-
NITRO-1,3-DIPHENYL-2-PROPEN- 1-ONE: SYNTHESIS OF QUINOLINES, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 32:23, 3617-3620, DOI: 10.1081/SCC-120014974
To link to this article: http://dx.doi.org/10.1081/SCC-120014974
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 23, pp. 3617–3620, 2002
SAMARIUM DIIODIDE MEDIATED
REDUCTIVE COUPLING OF
2-NITRO-1,3-DIPHENYL-2-PROPEN-
1-ONE: SYNTHESIS OF QUINOLINES
Xiaoxia Wang1 and Yongmin Zhang1,2,
*
1Department of Chemistry, Zhejiang University
(Campus Xixi), Hangzhou, 310028, P.R. China
2State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai, 200032, P.R. China
ABSTRACT
The intramolecular reductive cyclization of 2-nitro-1,3-diphe-
nyl-2-propen-1-ones (1) induced by SmI2 was investigated and
2-arylquinolines (2) were obtained in moderate to good yields
at room temperature under neutral conditions.
Key Words: Samarium diiodide; Reductive coupling; Intra-
molecular cyclization; Quinolines; Synthesis
Herein we wish to report the synthesis of 2-arylquinolines by the
intramolecular reductive coupling of o-nitrochalcones promoted by SmI2
at room temperature under neutral conditions (Sch. 1).
Table 1 summarizes our results on the intramolecular reductive cycli-
zation of 2-nitro-1,3-diphenyl-2-propen-1-ones induced by SmI2. Chloro,
*Corresponding author. Fax: 86-571-88807077; E-mail: yminzhang@mail.hz.zj.cn
3617
DOI: 10.1081/SCC-120014974
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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3618
WANG AND ZHANG
Scheme 1.
Table 1. The Synthesis of 2-Arylquinolines Promoted by SmI2
Yield*
(%)
Entry
R1
R2
R
2a
2b
2c
2d
2e
2f
2g
2h
2i
H
H
H
H
H
H
H
H
H
H
C6H5
65
70
62
73
65
70
62
65
—
p-CH3C6H4
p-ClC6H4
p-BrC6H4
p-CH3OC6H4
C6H5
p-CH3C6H4
p-BrC6H4
CH3
–OCH2O–
–OCH2O–
–OCH2O–
H
H
*Isolated yield.
bromo, alkoxy groups bearing on the benzene rings are tolerated under the
reaction conditions and have no obvious influence on the rate of intramo-
lecular reductive cyclization. Though ordinary chalcones were reported to
give the cyclodimerization products in good yields under SmI2 conditons,[1]
the o-nitrochalcones here afforded the quinolines as the main products
rather than cyclodimerization ones. The intramolecular cyclization com-
pletes in 2–3 h at room temperature. When 1-methyl-3-(20-nitrophenyl)-2-
propen-1-one (Entry 2i) was treated by SmI2, the predicted product
2-methylquinoline could not be obtained.
In conclusion, 2-arylquinolines are readily obtained via intramolecular
reductive cyclization of 2-nitro-1,3-diphenyl-2-propen-1-ones by samarium
diiodide. The advantages of the present procedure are convenient manipula-
tion, easy availability of starting materials and mild reaction conditions.
EXPERIMENTAL
Tetrahydrofuran was distilled from sodium–benzophenone ketyl
immediately prior to use. All reactions were conducted under a nitrogen

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2-NITRO-1,3-DIPHENYL-2-PROPEN-1-ONE
3619
atmosphere. Melting points are uncorrected. 1H NMR spectra were
recorded on a Bruker AC 80spectrometer as CDCl solutions using TMS
3
as internal standard. Chemical shifts (ꢀ) are reported in ppm. IR spectra
were recorded using KBr disks with a Bruker Vector-22 infrared spectrom-
eter. Metallic samarium and all solvents were purchased from commercial
sources, without further purification before use.
General Procedure for the Synthesis of 2-Arylquinolines
A solution of 2-nitrochalcones (1) (1 mmol) in anhydrous THF (3 mL)
was added dropwise to the solution of 6 mmol SmI2 in dry THF (30mL) at
room temperature under a nitrogen atmosphere. At completion (monitored
by TLC), the reaction mixture was quenched with 0.1 N HCl (3 mL) and
extracted with diethyl ether (3 Â 15 mL). The combined extracts were
washed with a saturated solution of NaCl (15 mL) and dried over anhydrous
Na2SO4. After evaporation of the solvent under reduced pressure, the crude
products 2a–i were purified by preparative TLC on silica gel using ethyl
acetate–cyclohexane (1 : 8) as eluent.
2-Phenylquinoline (2a): Light yellow crystals, m.p. 80–82ꢀC (lit[2]
83ꢀC). IR (KBr): ꢁmax (cmÀ1) 1620(C ¼N). H NMR (CDCl3): ꢀ (ppm)
1
7.23–8.24 (m, ArH).
2-( p-Methylphenyl)quinoline (2b): Light yellow crystals, m.p. 78–80ꢀC
(lit[2] 81–82ꢀC). IR (KBr): ꢁmax (cmÀ1) 1620(C ¼N). H NMR (CDCl3): ꢀ
1
(ppm) 2.41 (3H, s, ArCH3), 7.12–8.22 (10H, m, ArH).
2-( p-Chlorophenyl)quinoline (2c): Light yellow crystals, m.p. 107–109ꢀC
(lit[3] 112ꢀC). IR (KBr): ꢁmax (cmÀ1) 1615 (C¼N). 1H NMR (CDCl3): ꢀ (ppm)
7.15–8.12 (m, ArH).
2-( p-Bromophenyl)quinoline (2d): Light yellow crystals, m.p. 120–122ꢀC
(lit[3] 123–124ꢀC). IR (KBr): ꢁmax (cmÀ1) 1615 (C¼N). H NMR (CDCl3): ꢀ
1
(ppm) 7.23–8.11 (m, ArH).
2-( p-Methoxyphenyl)quinoline (2e): Light yellow crystals, m.p.
120–122ꢀC (lit[2] 122–123ꢀC). IR (KBr): ꢁmax (cmÀ1) 1620(C ¼N).
1H NMR (CDCl3): ꢀ (ppm) 3.88 (3H, s, ArOCH3), 6.91–8.25 (10H, m, ArH).
2-Phenyl-6,7-methylenedioxy-quinoline (2f): Light yellow crystals, m.p.
144–146ꢀC (lit[4] 146–148ꢀC). IR (KBr): ꢁmax (cmÀ1) 1620(C ¼N). 1H NMR
(CDCl3): ꢀ (ppm) 6.10(2H, s, ArOC H2O), 7.05–8.10 (9H, m, ArH).
MS : m/z (%) 249 (Mþ, 100).
2-( p-Methylphenyl)-6,7-methylenedioxy-quinoline (2g): Light yellow
crystals, m.p. 110–111ꢀC (lit[4] 122–114ꢀC). IR (KBr): ꢁmax (cmÀ1) 1620
(C¼N). 1H NMR (CDCl3): ꢀ (ppm) 2.05 (3H, s, ArCH3), 6.09 (2H, s,
ArOCH2O), 7.06–8.12 (8H, m, ArH). MS : m/z (%) 263 (Mþ, 100).

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3620
WANG AND ZHANG
2-( p-Bromophenyl)-6,7-methylenedioxy-quinoline (2h): Light yellow
crystals, m.p. 201–202ꢀC (lit[4] 202–204ꢀC). IR (KBr): ꢁmax (cmÀ1) 1625
(C¼N). 1H NMR (CDCl3): ꢀ (ppm) 6.11 (2H, s, ArOCH2O), 7.12–8.30
(8H, m, ArH). MS : m/z (%) 327 (Mþ, 100).
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 Netherlands November 22, 2001