A highly stereoselective synthesis of 2,3,4,5-tetrasubstituted-trans-2,3-dihydrofurans

Article abstract of DOI:10.1081/SCC-120030747

α,β-Unsaturated sulfones derivatives 5 was prepared from sodium p-toluenesulfinate (1) and the products reacted with substituted-carbomethoxymethyltriphenylarsonium bromide 6 in the presence of potassium carbonate at room temperature to give cyclopropane derivatives 2-substituted-3-substitutedphenyl-4-p-toluenesulfonyl-5-phenyl-trans-2, 3-dihydrofurans 7 and/or 8 with high stereoselectivity.

Full text of DOI:10.1081/SCC-120030747

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A Highly Stereoselective Synthesis of
2,3,4,5‐Tetrasubstituted‐trans‐2,3‐dihydrofurans
Weiguo Cao a b , Weiyu Ding a , Jie Chen a , Yali Chen a , Qin Zang a & Guodong Chen a
a Department of Chemistry , Shanghai University , Shanghai, 200436, P.R. China
b State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic
Chemistry, Chinese Academy of Science , Shanghai, P.R. China
Published online: 16 Aug 2006.
To cite this article: Weiguo Cao , Weiyu Ding , Jie Chen , Yali Chen , Qin Zang & Guodong Chen (2004) A Highly
Stereoselective Synthesis of 2,3,4,5‐Tetrasubstituted‐trans‐2,3‐dihydrofurans, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 34:9, 1599-1608, DOI: 10.1081/SCC-120030747
To link to this article: http://dx.doi.org/10.1081/SCC-120030747
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 9, pp. 1599–1608, 2004
A Highly Stereoselective Synthesis of 2,3,4,5-
Tetrasubstituted-trans-2,3-dihydrofurans
1
1
1
Weiguo Cao,1,2, Weiyu Ding, Jie Chen, Yali Chen,
*
Qin Zang,1 and Guodong Chen1
1Department of Chemistry, Shanghai University, Shanghai, P.R. China
2State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Science,
Shanghai, P.R. China
ABSTRACT
a,b-Unsaturated sulfones derivatives 5 was prepared from sodium
p-toluenesulfinate (1) and the products reacted with substituted-
carbomethoxymethyltriphenylarsonium bromide 6 in the presence of
potassium carbonate at room temperature to give cyclopropane deri-
vatives 2-substituted-3-substitutedphenyl-4-p-toluenesulfonyl-5-phenyl-
trans-2,3-dihydrofurans 7 and/or 8 with high stereoselectivity.
Key Words: Stereoselective synthesis; a,b-Unsaturated sulfones;
Dihydrofurans derivatives; Arsonium bromide.
*
Correspondence: Weiguo Cao, Department of Chemistry, Shanghai University,
Shanghai 200436, P.R. China; Fax: þ86-21-66134856; E-mail: wgcao@mail.shu.
edu.cn.
1599
DOI: 10.1081/SCC-120030747
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Cao et al.
INTRODUCTION
Some natural products with furanoid or hydrofuranoid moiety show
biological activity.[1] Recently, hydrofuran derivatives have been extensively
studied because of their potential importance in the synthesis of antivirus and
antitumour pharmaceuticals and anti-AIDS nucleosides.[2] The present paper
covers the reaction of a,b-unsaturated sulfones 5 with arsonium bromide 6
in the presence of potassium carbonate at room temperature to afford
2,3,4,5-tetrasubstituted-trans-2,3-dihydrofurans 7 and/or 8 via Micheal
addition with high stereoselectivity. And the preparation of a series of
a,b-unsaturated sulfone derivatives 5 via Knoevenagel condensation was
also reported in this paper.
Scheme 1.
Table 1. Preparation of compound 5.
Compound
Yield (%)
M.p. (8C)
Compound
Yield (%)
M.p. (8C)
5a
5b
5c
5d
5e
5f
78
87
89
85
88
85
75
130.8–132.2
138.2–138.5
127.0–127.7
135.1–135.7
213.6–213.6
159.9–160.0
158.9–159.0
5h
5i
79
81
93
87
94
87
89
142.4–142.5
169.3–170.3
141.5–141.8
163.1–164.0
148.0–148.2
159.4–159.6
186.6–186.8
5j
5k
5l
5m
5n
5g

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2,3,4,5-Tetrasubstituted-trans-2,3-dihydrofurans
1601
Scheme 2.
RESULTS AND DISCUSSION
Sodium p-toluenesulfinate (1) reacted with v-bromobenzopheonone (2)
in the presence of phase transfer catalyst tetrabutylammonium bromide to
give 2-(p-toluenesulfonyl)acetophenone (3). Compound 3 reacted further
with aromatic aldehydes 4a–n in anhydrous benzene in the presence of piper-
idine and glacial acetic acid to give a,b-unsaturated sulfones 5a–n in high
yields (Sch. 1). The results are illustrated in Table 1.
Figure 1. X-ray structure of compound 7Ig.

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Cao et al.
Figure 2. X-ray structure of compound 8Ig.
Table 2. Preparation of compounds 7 and 8.
Y
X
Product
M.p. (8C)
Yield (%)
Ph
CH3
H
7Ig
7Ih
7Im
7In
167.3–167.5
157.4–157.6
147.8–148.7
191.9–192.5
64
57
70
55
Cl
NO2
CH3O
CH3
CH3
H
7IIg
7IIh
7IIm
7IIn
94.8–95.7
100.9–100.9
103.2–104.2
103.0–103.6
55
53
58
61
Cl
NO2
CH3
H
8IIIg
8IIIh
8IIIm
8IIIn
146.4–147.0
102.6–103.7
146.7–148.1
233.4–234.4
69
56
64
73
Cl
NO2

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1603
y
d

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Cao et al.
y
d

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2,3,4,5-Tetrasubstituted-trans-2,3-dihydrofurans
1605

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Cao et al.
y
d

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2,3,4,5-Tetrasubstituted-trans-2,3-dihydrofurans
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a,b-Unsaturated sulfones 5g,h,m,n (X ¼ p-CH3, H, p-Cl, p-NO2) reacted
with arsonium bromide 6I–III (Y ¼ Ph, CH3O, CH3) in CH2Cl2 in the presence
of potassium carbonate at room temperature for 24hr to give 2-substituted-3-
substitutedphenyl-4-p-toluenesulfonyl-5-phenyl-trans-2,3-dihydrofurans 7Ig–IIn
and/or 8IIIg–n with high stereoselectivity (Sch. 2).
In fact, when benzoylmethyltriphenylasonium bromide (I) or carbo-
methoxymethyl triphenysonium bromide (II) was used as the reactants, the
main product was dihydrofurans 7 (Fig. 1). If excess arsonium bromide was
used, some dihydrofurans 8 was also produced as products (e.g., 8Ig,
,10%, Fig. 2). When acetylmethyltriphenylarsonium bromide (III) was
used as the reactant, the main product was dihydrofurans 8. The reaction
could not stop at the step of product 7. The results are illustrated in Table 2.
The structures of compounds 5, 7, and 8 were confirmed by means of
microanalyses, 1H-NMR, MS, IR (Table 3). The configurations of compounds
7 and 8 were determined by x-ray diffraction as shown in Figs. 1 and 2.
The reaction mechanism was proposed as Sch. 3. The double bond in the
a,b-unsaturated sulfones 5 was attacked nucleophilically by the carbanion
derived from arsonium bromide to yield an intermediate with two chiral
carbon atoms C1 and C2. And then an intramolecular nucleophilic substitu-
tion reaction occurred. There were two possibilities when the oxygen atom
attacked the C2 from the backside of leaving group (Ph3As) like A and B in
the Sch. 3. As the intermediate A is more stable than B in which the repulsion
Scheme 3.

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Cao et al.
of two large groups existed. So the reaction preferred the intermediate A to
produce the trans-form products.
EXPERIMENTAL
Melting points are uncorrected and were recorded on a WRS-1 melting
point apparatus. IR spectra were measured on a 7400 spectrometer (Shanghai
Analytical Instrument Factory, China) with KBr discs. NMR spectra were
taken from an AC-300SC spectrometers, using solutions in CDCl3 as the
internal standard. J values are given in Hz. Mass spectra were run on a HP
5989A spectrometer. Microanalyses were measured with a Foss Heraeus
CHN-O-PAPID element analysis instrument.
2-(p-Toluenesulfonyl)acetophenone (3)[3] and a,b-unsaturated sulfones
derivatives 5[4] was prepared as described in the literature.
2,3,4,5-Tetrasubstituted-trans-2,3-dihydrofurans 7, 8 (general procedure):
1 mmol a,b-unsaturated sulfones 5, 1 mmol arsonium bromide 6 [2 mmol
for methylcarbonyl-methylenetriphenylarsonium bromide (III)], and 2 mmol
potassium carbonate were added into 5 mL dichloromethane. Stirring for 24hr,
the insoluble material was filtered-off and the solvent was evaporated under
reduced pressure. The residue was purified by passing through a silica gel thin
plate (GF254, 200–300 m) with petroleum ether–ethyl acetate (v: v ¼ 8 : 1)
as developing agent and the title compounds 7 or 8 were obtained. Further
purification for solid samples can be carried out by recrystallization from ethyl
acetate/petroleum ether.
ACKNOWLEDGMENT
Thanks are due to the National Science Foundation of China for financial
support.
REFERENCES
1. Dulere, J.P.; Baret, N.; Rodriguez, J. J. Chem. Soc. Chem. Commun. 1994, 303.
2. Sugimura, H.; Osumi, K.; Kodaka, Y.; et al. J. Org. Chem. 1994, 59 (7), 653.
3. Wildeman, J.; Van Leusen, A.M. Synthetic Commun. 1979, 733.
4. Eistert, B.; Geiss, F. Chem. Ber. 1961, 94, 929.
Received in the UK May 7, 2003

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