A facile stereoselective synthesis of (Z)-α-arylsulfonyl-α,β-unsaturated ketones

Article abstract of DOI:10.1016/j.tet.2009.06.072

Palladium-catalyzed hydrostannylation of acetylenic sulfones 1 in benzene at room temperature gives highly regio- and stereoselectively (E)-α-stannylvinyl sulfones 2 in high yields. (E)-α-Stannylvinyl sulfones 2 are new difunctional group reagents which u

Full text of DOI:10.1016/j.tet.2009.06.072

Tetrahedron 65 (2009) 6863–6867
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A facile stereoselective synthesis of (Z)-a-arylsulfonyl-a,b-unsaturated ketones
,
,
Shengyong You a b, Jianying Li c, Mingzhong Cai a
*
a Department of Chemistry, Jiangxi Normal University, Nanchang 330022, PR China
b Institute of Applied Chemistry, Jiangxi Academy of Science, Nanchang 330029, PR China
c Department of Chemistry, Jingdezhen Comprehensive College, Jingdezhen, Jiangxi 333000, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 April 2009
Received in revised form 14 June 2009
Accepted 19 June 2009
Available online 24 June 2009
Palladium-catalyzed hydrostannylation of acetylenic sulfones 1 in benzene at room temperature gives
highly regio- and stereoselectively (E)- -stannylvinyl sulfones 2 in high yields. (E)- -Stannylvinyl sul-
fones 2 are new difunctional group reagents which undergo Stille coupling reactions with acyl chlorides
3 to afford stereoselectively (Z)- -arylsulfonyl- -unsaturated ketones 4 in good yields. A one-pot
stereoselective synthesis of (Z)- -arylsulfonyl- -unsaturated ketones 4 has also been achieved by
a
a
a
a
a,b
a,b
tandem hydrostannylation-Stille coupling reaction of acetylenic sulfones 1 under mild conditions.
Keywords:
Hydrostannylation
Palladium
Ó 2009 Elsevier Ltd. All rights reserved.
Stille coupling
Tandem reaction
Acyl chloride
1. Introduction
compounds7 or through palladium-catalyzed acylation of (E)-
selanylvinylstannanes with acyl halides.8 Some methods for the
synthesis of -aryl(alkyl)thio- -unsaturated ketones have been
a-
a
,b
-Unsaturated ketones are one of the most widely used syn-
thetic building blocks and a variety of synthetic methods for the
synthesis of -unsaturated ketones have been reported. Of these
a
a,b
developed including Pummerer rearrangement of 2-arylsulfinyl
a
,b
ketones,9–11 the NaOH-catalyzed thiolysis of
and the Rh-catalyzed diazo decomposition of
ketones.13
a
b
,
b
-epoxyketones,12
-thio group -diazo
methods, the aldol condensation is one of the most powerful syn-
thetic tools for them.1,2 The Friedel–Crafts reaction of acyl chlorides,
acids, or anhydrides with olefins is also an important route to the
a
Recently, a-arylsulfonyl-a,b-unsaturated ketones have attracted
a
,b
-unsaturated ketones.3 The hydrozirconation of alkynes, fol-
considerable interest because of their utility as synthetic in-
termediates, particularly for the synthesis of heterocyclic sys-
lowed by aluminum chloride promoted acylation of the resulting
vinylzirconium compounds, has provided a convenient method for
stereoselective synthesis of
tems.14–19
A
common route to -unsaturated
ketones involves the Knoevenagel condensation of -keto sulfones
with aldehydes.20–22 Alternatively,
-arylsulfonyl-a,b-unsaturated
a
-arylsulfonyl-
a
b
,
b
a
,b
-unsaturated ketones.4 The synthe-
sis of functionalized -unsaturated ketones is also of considerable
a
,b
a
interest in organic synthesis because they are important in-
termediates in the synthesis of a wide variety of organic com-
pounds. Sung et al. reported that hydrozirconation of acetylenic
tellurides, followed by the reaction with acyl halides in the pres-
ketones can also be obtained via peracid oxidation of 4-arylsul-
fonyl-substituted 4-isoxazolines.23 However, the stereoselective
synthesis of
less attention. (E)-
synthesized by utilizing either a reaction of
fones with acyl chlorides24 or
reaction of a
a
-arylsulfonyl-
a
,
b
-unsaturated ketones has received
-unsaturated ketones can be
-lithiated vinyl sul-
-arylsulfonyl-
a-Arylsulfonyl-
a,b
ence of CuI, gave
et al. described the synthesis of (Z)-
ketones by CuX-catalyzed selenocarbonylation addition reaction of
selenoesters to nonactivated terminal alkynes.6 (Z)-
-Selenyl-
unsaturated ketones could be prepared by utilizing either a Wittig-
type reaction of -phenylselanyl arsonium ylides with carbonyl
a
-organotelluro-
a
,b
-unsaturated ketones.5 Zhao
-selenyl- -unsaturated
a
b
a
,b
a
substituted alkenylmagnesium reagents with acyl chlorides in the
presence of stoichiometric amount of CuCN$2LiCl.25 To the best of
our knowledge, no well-established method has been used to
a
a,b-
a
prepare
stereoselectively
(Z)-
a-arylsulfonyl-
a
,b
-unsaturated
ketones to date. Herein we wish to report that (Z)-
a-arylsulfonyl-
a,b-unsaturated ketones can be conveniently synthesized by pal-
ladium-catalyzed hydrostannylation of acetylenic sulfones,
followed by the Stille coupling with acyl halides in the presence of
a catalytic amount of Pd(PPh3)4 and CuI cocatalyst.
* Corresponding author. Tel./fax: þ86 791 8120388
E-mail address: mzcai@jxnu.edu.cn (M. Cai).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.06.072

6864
S. You et al. / Tetrahedron 65 (2009) 6863–6867
Table 1
2. Results and discussion
Stille coupling reaction of (E)-1-phenylsulfonyl-1-tributylstannyl-1-hexene with
benzoyl chloridea
Palladium-catalyzed hydrostannylation of alkynes provides
a simple general route for the synthesis of vinylstannanes.26 In
1991, Magriotis reported that the palladium-catalyzed hydro-
stannylation of phenylthioalkynes with Bu3SnH was highly regio-
C4H9
H
SO2Ph
O
C
C4H9
SO2Ph
Cat.
Ph
+
C
SnBu3
H
Ph
Cl
O
and stereoselective, giving (E)-a-stannylvinyl sulfides in high
yields.27 Paley et al. reported that the palladium-catalyzed hydro-
Catalystb
Additivec
Solvent
Temp (ꢁC)
Time (h) Yieldd (%)
stannylation of chiral alkynyl sulfoxides at ꢀ78 ꢁC was also highly
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdBnCl(PPh3)2
PdBnCl(PPh3)2
PdBnCl(PPh3)2
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
DMF
C6H6
C6H6
THF
rt (or 65 ꢁC)
rt (or refux)
120 (sealed tube)
rt (or refux)
120 (sealed tube)
rt (or 65 ꢁC)
120 (sealed tube)
120 (sealed tube)
rt (or 65 ꢁC)
120 (sealed tube)
rt
Reflux
Reflux
120 (sealed tube)
Reflux or 120
Reflux or 120
72
72
72
72
72
72
72
72
72
72
72
4
0
0
12
0
0
regio- and stereoselective, affording chiral (E)-a-stannylvinyl sulf-
oxides in good yields.28 Huang et al. demonstrated that alkynyl
selenides can also undergo the palladium-catalyzed hydro-
THF
stannylation to afford stereoselectively (E)-a-stannylvinyl
selenides.29 Xiang et al. reported that palladium-catalyzed hydro-
stannylation of acetylenic triflones with tributyltin hydride
DMF
C6H6
THF
DMF
THF
C6H6
C6H6
C6H6
C6H6
C6H6
C6H6
0
22
Trace
0
0
0
79
84
85
0
provided
a-stannylated vinyl triflones regiospecifically, but the
reaction was not stereospecific, affording a 1:1.7 ratio of E and Z
stereoisomers.30 Recently, we investigated the palladium-catalyzed
hydrostannylation of acetylenic sulfones in order to prepare (E)-a-
7
7
72
72
stannylvinyl sulfones. We found that the hydrostannylation re-
action of acetylenic sulfones with tributyltin hydride proceeded
smoothly in benzene in the presence of catalytic amount of
Pd(PPh3)4
Pd(PPh3)4
CuI
0
a
Pd(PPh3)4 at room temperature to afford the corresponding (E)-a-
Reaction was carried out with 1.0 mmol of (E)-1-phenylsulfonyl-1-tributyl-
stannyl-1-hexene and 1.1 mmol of benzoyl chloride in solvent (2 mL) under Ar.
stannylvinyl sulfones in high yields with high regio- and stereo-
selectivities (Scheme 1). Investigations of the crude products 2 by
1H NMR spectroscopy (400 MHz) showed their isomeric purities of
more than 98%. One olefinic proton signal of compounds 2a and 2b
b
5 mol % of Pd catalyst was used.
0.75 equiv CuI was used.
c
d
Isolated yield.
splits characteristically into one triplet at
d
¼6.25–6.28 with cou-
among those tested, such as DMF and THF. The cross-coupling re-
action proceeded smoothly in benzene at reflux temperature in the
presence of 5 mol % Pd(PPh3)4 and 75 mol % CuI, affording
the corresponding coupled product in 84% yield after 7 h; while the
same reaction under sealed-tube conditions gave the coupled
product in 85% yield. In general, the amount of Pd(PPh3)4 and CuI in
their co-catalyzed organic transformation only is less than
10 mol %. However, we found that the amount of CuI affected the
reaction rate of the Stille coupling. When 10 mol % CuI was used as
the co-catalyst, the cross-coupling reaction of benzoyl chloride
(1.1 equiv) with (E)-1-phenylsulfonyl-1-tributylstannyl-1-hexene
in benzene at reflux temperature in the presence of 5 mol %
Pd(PPh3)4 proceeded slowly, giving the coupled product in only 47%
yield after 48 h. The reaction did not occur in the presence of
Pd(PPh3)4 without the co-catalyst (CuI) after 72 h even under
sealed-tube conditions. On the other hand, the reaction did not also
occur in the presence of CuI without any palladium catalyst.
pling constant J¼7.2 Hz, which indicated that the hydro-
stannylation to the acetylenic sulfones had taken place with strong
preference for the addition of the tin atom at the carbon adjacent to
the sulfonyl group. The stereochemistry of the addition was readily
apparent from the 1H NMR spectra of compounds 2 which showed
a (3JSn117–H) coupling constant of 52 Hz, fully in accord with an E
geometry and overall cis addition of tin hydride.31
SO2Ar
SnBu3
R
H
Pd(PPh3)4 (1 mol %)
Benzene, rt
+ Bu3SnH
R
SO2Ar
1
2
2a: R = C4H9, Ar = Ph, 90%
2b: R = C4H9, Ar = 4-MePh, 88%
2c: R = Ph, Ar = Ph, 82%
Scheme 1.
(E)-a-Stannylvinyl sulfones 2 are difunctional group reagents in
The Stille coupling reactions of (E)-a-arylsulfonylvinylstannanes
which two synthetically versatile groups are linked to the same
olefinic carbon atom and can be considered both as vinylstannanes
and as vinyl sulfones. Vinylstannanes can undergo the Stille cou-
pling reaction with organic electrophiles.32 Huang et al. reported
with a variety of acyl halides were examined in the presence of
a catalytic amount (5 mol %) of Pd(PPh3)4 and CuI (0.75 equiv) in
benzene at reflux temperature (Scheme 2) and the results are
summarized inTable 2. In all cases, the reaction proceeded smoothly
palladium-catalyzed acylation reaction of (E)-
stannanes with acyl halides, providing a new route for the stereo-
selective synthesis of (Z)- -selenyl-
-unsaturated ketones.8
However, to the best of our knowledge, there has been no general
study of Stille coupling of (E)- -arylsulfonylvinylstannanes with
acyl halides described to date. With a convenient route to the (E)-
arylsulfonylvinylstannanes 2 we decided to establish the feasibility
of using 2 in cross-coupling reactions with acyl halides 3. Initially,
to determine the optimum conditions, the cross-coupling reaction
of benzoyl chloride (1.1 equiv) with (E)-1-phenylsulfonyl-1-tribu-
tylstannyl-1-hexene was examined under various reaction
conditions. The results are summarized in Table 1. Among the
palladium–phosphine complexes screened, Pd(PPh3)4 showed
the best catalytic activity (yield 84%); while the yields were low in
the presence of other palladium–phosphine complexes such as
PdCl2(PPh3)2 (12%) and PdBnCl(PPh3)2 (22%) even under sealed-
tube conditions. It was found that benzene was the best solvent
a-selanylvinyl-
to afford the corresponding (Z)-a-arylsulfonyl-a,b-unsaturated ke-
tones in good yields. Electron donating and electron withdrawing
groups such as CH3, CH3O, Cl, NO2 on aromatic acyl halides were
a
a,b
well tolerated. Unfortunately, the Stille coupling of (E)-a-arylsulfo-
a
nylvinylstannanes with aliphatic acyl halides did not occur under
the same conditions. It is well documented that the Stille coupling
reaction of vinylstannanes with organic halides, in the presence of
a palladium catalyst, occurs with retention of configuration.32 In
addition, the Z-configuration of compound 4d was confirmed by
NOESY experiments. An enhancement of the allylic protons was
a
-
R
H
SO2Ar
O
C
Pd(PPh3)4/CuI
Benzene, reflux
R
H
SO2Ar
SnBu3
R1
+
C
R1
Cl
O
2
3
4
Scheme 2.

S. You et al. / Tetrahedron 65 (2009) 6863–6867
6865
observed as the vinylic proton of 4d was irradiated. A correlation
between the allylic protons and the aromatic protons (
(4-methylphenyl)sulfonyl group was observed. The NOE results
3. Conclusions
d
¼7.68) of
In summary, we have developed an efficient and stereoselective
one-pot method for the synthesis of (Z)- -arylsulfonyl- -un-
indicate that compound 4d has the expected Z-configuration and
a
a,b
that the cross-coupling reaction of (E)-
with acyl halides occurs with retention of configuration.
a
-arylsulfonylvinylstannanes
saturated ketones by the tandem hydrostannylation-Stille coupling
reactions of acetylenic sulfones with tributyltin hydride and acyl
chlorides. The present method has the advantages of readily
available starting materials, straightforward and simple pro-
cedures, mild reaction conditions and good yields.
Table 2
Synthesis of (Z)-
a
-arylsulfonyl-
a
,
b
-unsaturated ketonesa
Entry
R
Ar
R1
Product
Yieldb (%)
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
Ph
Ph
Ph
4a
4b
4c
4d
4e
4f
4g
4h
4i
84
80
81
79
82
81
84
85
87
86
84
78
4. Experimental
4.1. Materials
4-CH3C6H4
Ph
4-CH3C6H4
Ph
4-O2NC6H4
4-ClC6H4
4-ClC6H4
4-O2NC6H4
4-CH3C6H4
4-CH3OC6H4
Ph
4-ClC6H4
4-O2NC6H4
4-CH3C6H4
4-CH3C6H4
All chemicals were of reagent grade and used as purchased.
Benzene and THF were distilled from sodium prior to use. DMF was
dried by distillation over calcium hydride. All reactions were car-
ried out in pre-dried glassware (150 ꢁC, 4 h) and cooled under
a stream of dry Ar. IR spectra were determined on a Perkin–Elmer
683 instrument. 1H NMR spectra were recorded on a Bruker AC-
P400 (400 MHz) spectrometer with TMS as an internal standard in
CDCl3 as solvent. 13C NMR spectra were recorded on a Bruker AC-
P400 (100 MHz) spectrometer in CDCl3 as solvent. Mass spectra
were determined on a Finnigan 8230 mass spectrometer. Micro-
analyses were measured using a Yanaco MT-3 CHN microelemental
analyzer.
Ph
Ph
Ph
Ph
Ph
Ph
9
10
11
12
Ph
Ph
Ph
4j
4k
4l
a
Reaction was carried out with 1.0 mmol of (E)-a-arylsulfonylvinylstannane,
1.1 mmol of acyl chloride, 0.05 mmol of Pd(PPh3)4, and 0.75 mmol of CuI in benzene
(2 mL) at reflux under Ar.
b
Isolated yield based on the (E)-a-arylsulfonylvinylstannane 2 used.
The tandem reaction has recently been of interest for organic
synthesis because it offers a convenient and economical method to
prepare desired organic molecules.33–35 Recently, Huang et al.
described the synthesis of functionalized allylic alcohols by
Michael-aldol tandem reaction of acetylenic sulfones with phe-
nylselenomagnesium bromides and aldehydes.36 Considering the
fact that both the hydrostannylation and Stille reactions were cat-
alyzed by Pd(PPh3)4, we tried to combine the two reactions in one
4.2. General procedure for the hydrostannylation
of acetylenic sulfones
A
25 mL, two-necked, round-bottom flask equipped with
a magnetic stir bar, and argon was charged sequentially with
acetylenic sulfone (1 mmol), benzene (4 mL), Pd(PPh3)4
pot to prepare stereoselectively (Z)-a-arylsulfonyl-a,b-unsaturated
1
ketones (Scheme 3). We found that, after the hydrostannylation
reaction of acetylenic sulfones 1 with Bu3SnH using 5 mol %
Pd(PPh3)4 in benzene at room temperature for 2 h, acyl chlorides
and 75 mol % CuI were added and the resulting mixture was stirred
(0.01 mmol) and Bu3SnH (1.05 mmol). The mixture was stirred at
room temperature for 4 h. After removal of the solvent under re-
duced pressure, the residue was diluted with light petroleum ether
(20 mL) and filtered to remove the palladium catalyst. The resulting
solution was concentrated under vacuum and the residue was
purified by flash chromatography on silica gel (eluent: light pe-
troleum ether/Et2O, 7:1).
at reflux for 7–10 h, the desired (Z)-a-arylsulfonyl-a,b-unsaturated
ketones 4 were obtained in good yields. The experimental results
are summarized in Table 3. As shown in Table 3, the hydro-
stannylation–Stille tandem reaction of acetylenic sulfones with
Bu3SnH and a variety of acyl chlorides proceeded smoothly under
very mild conditions to afford stereoselectively the corresponding
4.2.1. (E)-1-Phenylsulfonyl-1-tributylstannyl-1-hexene (2a)
Oil. IR (film):
n
(cmꢀ1) 3066, 2958, 2927, 1713, 1587, 1446, 1285,
1138, 1082, 822, 689. 1H NMR (400 MHz, CDCl3):
d
7.86–7.84 (m,
(Z)-a-arylsulfonyl-a,b-unsaturated ketones 4.
SO2Ar
R
H
SO2Ar
SnBu3
R
H
R1COCl (3), CuI
Bu3SnH, Pd(PPh3)4
R1
C
R
SO2Ar
Benzene, rt
Benzene, reflux
2
1
4
O
Scheme 3.
3
2H), 7.56–7.48 (m, 3H), 6.28 (t, J¼7.2 Hz, JSn–H¼52 Hz, 1H), 2.40–
2.36 (m, 2H), 1.56–1.48 (m, 6H), 1.38–1.29 (m, 6H), 1.22–1.15 (m,
4H), 1.11–1.06 (m, 6H), 0.90 (t, J¼7.2 Hz, 9H), 0.80 (t, J¼7.2 Hz, 3H).
Table 3
One-pot synthesis of (Z)-
a
-arylsulfonyl-
a
,
b
-unsaturated ketonesa
R1
Product
Ph
Entry
R
Ar
Yieldb (%)
13C NMR (100 MHz, CDCl3):
d 157.42, 149.03, 143.51, 132.50, 128.84,
1
2
3
4
5
6
7
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
Ph
4a
4b
4d
4f
79
76
73
75
81
80
71
127.13, 31.04, 30.62, 28.81, 27.32, 22.34, 13.80, 13.73, 11.40. MS (EI,
70 eV): m/z 513 (Mþ, 1.2), 457 (16), 291 (11), 197 (18), 111 (27), 73
(100). Anal. Calcd for C24H42SO2Sn: C, 56.19; H, 8.19. Found: C,
55.89; H, 8.02.
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
Ph
Ph
Ph
Ph
4-ClC6H4
4-O2NC6H4
4-CH3OC6H4
4-ClC6H4
4-CH3C6H4
4h
4j
4l
Ph
4.2.2. (E)-1-(p-Tolylsulfonyl)-1-tributylstannyl-1-hexene (2b)
a
Reaction was carried out with 1.0 mmol of acetylenic sulfone, 1.05 mmol of
Bu3SnH, 1.1 mmol of acyl chloride, 0.05 mmol of Pd(PPh3)4, and 0.75 mmol of CuI in
benzene (3 mL) under Ar.
Oil. IR (film):
n
(cmꢀ1) 2957, 2926, 1588, 1456, 1285, 1138, 1082,
812, 665. 1H NMR (400 MHz, CDCl3):
J¼8.4 Hz, 2H), 6.25 (t, J¼7.2 Hz, JSn–H¼52 Hz, 1H), 2.42 (s, 3H),
d
7.73 (d, J¼8.4 Hz, 2H), 7.29 (d,
b
3
Isolated yield based on the acetylenic sulfone 1 used.

6866
S. You et al. / Tetrahedron 65 (2009) 6863–6867
2.41–2.34 (m, 2H), 1.57–1.49 (m, 6H), 1.36–1.30 (m, 6H), 1.22–1.16
(t, J¼8.0 Hz, 1H), 2.43 (s, 3H), 2.03–1.97 (m, 2H), 1.43–1.19 (m,
(m, 4H), 1.10–1.05 (m, 6H), 0.91 (t, J¼7.2 Hz, 9H), 0.81 (t, J¼7.2 Hz,
4H), 0.78 (t, J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 190.10,
3H). 13C NMR (100 MHz, CDCl3):
d
156.93, 149.34, 143.20, 140.63,
146.26, 144.80, 141.77, 141.17, 136.64, 134.76, 131.21, 129.78,
129.23, 128.40, 30.12, 29.51, 22.17, 21.68, 13.60. MS (EI, 70 eV):
m/z 376 (Mþ, 35Cl, 2.5), 235 (37), 177 (39), 120 (100), 91 (41).
Anal. Calcd for C20H21SO3Cl: C, 63.73; H, 5.62. Found: C, 63.44;
H, 5.38.
129.41, 127.23, 30.90, 30.71, 28.84, 27.33, 22.31, 21.50, 13.81, 13.74,
11.41. MS (EI, 70 eV): m/z 527 (Mþ,1.4), 471 (100), 469 (71), 213 (22),
211 (33), 209 (24), 91 (18). Anal. Calcd for C25H44SO2Sn: C, 56.98; H,
8.35. Found: C, 56.75; H, 8.09.
4.2.3. (E)-1-Phenylsulfonyl-1-tributylstannyl-2-phenylethene (2c)
4.3.5. (Z)-1-(4-Chlorobenzoyl)-1-phenylsulfonyl-1-hexene (4e)
Oil. IR (film):
NMR (400 MHz, CDCl3): d 7.85–7.80 (m, 4H), 7.64–7.44 (m, 5H), 7.23
Oil. IR (film):
n
(cmꢀ1) 3063, 2957, 2921, 1585, 1446, 1286, 1136,
n
(cmꢀ1) 2928, 1670, 1587, 1320, 1152, 1087, 813. 1H
1081, 878, 745. 1H NMR (400 MHz, CDCl3):
d
7.39 (d, J¼8.0 Hz, 2H),
7.27–7.09 (m, 9H), 1.67–1.61 (m, 6H), 1.43–1.37 (m, 6H), 1.27–1.22
(t, J¼7.6 Hz, 1H), 2.04–1.98 (m, 2H), 1.42–1.21 (m, 4H), 0.80 (t,
(m, 6H), 0.95 (t, J¼7.2 Hz, 9H). 13C NMR (100 MHz, CDCl3):
J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 189.93, 146.91, 141.50,
d
154.43, 149.72, 141.40, 135.31, 131.93, 128.91, 128.20, 127.94,
141.23, 139.68, 134.74, 133.72, 131.18, 129.26, 129.11, 128.35, 30.10,
29.69, 22.16, 13.58. MS (EI, 70 eV): m/z 362 (Mþ, 35Cl, 7.3), 177 (100),
109 (66). Anal. Calcd for C19H19SO3Cl: C, 62.88; H, 5.28. Found: C,
62.59; H, 5.37.
127.73, 127.41, 29.04, 27.32, 13.74, 11.92. MS (EI, 70 eV): m/z 533
(Mþ, 1.1), 477 (100), 475 (71), 199 (17), 197 (35), 195 (24), 102 (21).
Anal. Calcd for C26H38SO2Sn: C, 58.59; H, 7.13. Found: C, 58.32; H,
6.94.
4.3.6. (Z)-1-(4-Nitrobenzoyl)-1-(p-tolylsulfonyl)-1-hexene (4f)
4.3. General procedure for the Stille coupling reaction
Oil. IR (film):
n
(cmꢀ1) 2927, 1625, 1597, 1521, 1347, 1152, 1086,
848. 1H NMR (400 MHz, CDCl3):
d
8.11 (d, J¼8.8 Hz, 2H), 7.53 (d,
To a solution of (E)-
a-arylsulfonylvinylstannane (1.0 mmol) and
J¼8.4 Hz, 2H), 7.40 (d, J¼8.8 Hz, 2H), 7.23 (d, J¼8.4 Hz, 2H), 6.23 (t,
J¼7.6 Hz, 1H), 2.95–2.87 (m, 2H), 2.40 (s, 3H), 1.44–1.32 (m, 4H),
acyl chloride (1.1 mmol) in benzene (2.0 mL) under Ar, Pd(PPh3)4
(0.05 mmol) and CuI (0.75 mmol) were added, the resulting mix-
ture was stirred at reflux for 7 h, cooled to room temperature, and
diluted with light petroleum. The supernatant was filtered through
a short plug of silica gel and the filtrate evaporated. The residue was
purified by preparative TLC on silica gel to afford the corresponding
compounds.
0.95 (t, J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 190.67, 148.44,
147.72, 144.67, 142.58, 140.75, 137.55, 131.07, 129.72, 127.67, 123.19,
31.33, 28.60, 22.46, 21.63, 13.90. MS (EI, 70 eV): m/z 387 (Mþ, 1.2),
360 (11), 295 (15), 157 (50), 139 (61), 115 (70), 109 (100), 91 (32).
Anal. Calcd for C20H21NSO5: C, 62.00; H, 5.46. Found: C, 61.71; H,
5.23.
4.3.1. (Z)-1-Benzoyl-1-phenylsulfonyl-1-hexene (4a)
4.3.7. (Z)-1-(4-Methylbenzoyl)-1-phenylsulfonyl-1-hexene (4g)
Oil. IR (film):
n
(cmꢀ1) 2927, 1667, 1596, 1448, 1319, 1154, 732. 1H
Oil. IR (film):
NMR (400 MHz, CDCl3):
n
(cmꢀ1) 2928, 1669, 1597, 1446, 1320, 1152, 733. 1H
NMR (400 MHz, CDCl3):
d
7.89–7.82 (m, 4H), 7.64–7.59 (m, 2H),
d
7.83 (d, J¼7.6 Hz, 2H), 7.79 (d, J¼8.0 Hz,
7.54–7.44 (m, 4H), 7.24 (t, J¼7.6 Hz, 1H), 2.04–1.98 (m, 2H), 1.42–
2H), 7.63–7.48 (m, 3H), 7.27–7.24 (m, 2H), 7.20 (t, J¼7.6 Hz,1H), 2.42
1.36 (m, 2H), 1.27–1.22 (m, 2H), 0.76 (t, J¼7.2 Hz, 3H). 13C NMR
(s, 3H), 2.05–1.98 (m, 2H), 1.42–1.36 (m, 2H), 1.26–1.18 (m, 2H), 0.78
(100 MHz, CDCl3):
d
191.13, 146.82, 141.63, 139.84, 136.37, 134.52,
(t, J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 190.56, 146.41,
133.64, 129.82, 129.07, 128.86, 128.38, 30.09, 29.60, 22.16, 13.60. MS
(EI, 70 eV): m/z 328 (Mþ, 73), 187 (21), 105 (100). Anal. Calcd for
C19H20SO3: C, 69.48; H, 6.14. Found: C, 69.20; H, 6.03.
145.76, 141.77, 139.93, 133.98, 133.56, 130.02, 129.58, 129.03, 128.37,
30.13, 29.57, 22.18, 21.86, 13.63. MS (EI, 70 eV): m/z 342 (Mþ, 8.9),
119 (100), 91 (67). Anal. Calcd for C20H22SO3: C, 70.15; H, 6.48.
Found: C, 70.33; H, 6.34.
4.3.2. (Z)-1-Benzoyl-1-(p-tolylsulfonyl)-1-hexene (4b)
Oil. IR (film):
NMR (400 MHz, CDCl3):
n
(cmꢀ1) 2928, 1668, 1597, 1450, 1320, 1145, 717. 1H
4.3.8. (Z)-1-(4-Methoxybenzoyl)-1-phenylsulfonyl-1-hexene (4h)
d
7.90–7.88 (m, 2H), 7.70 (d, J¼8.4 Hz, 2H),
Oil. IR (film):
n
(cmꢀ1) 2926, 1667, 1596, 1445, 1318, 1150, 1109,
7.61 (t, J¼7.2 Hz, 1H), 7.46 (t, J¼7.6 Hz, 2H), 7.30 (d, J¼8.0 Hz, 2H),
7.20 (t, J¼7.6 Hz, 1H), 2.42 (s, 3H), 2.03–1.97 (m, 2H), 1.41–1.17 (m,
724. 1H NMR (400 MHz, CDCl3):
d 7.89–7.81 (m, 4H), 7.63–7.49 (m,
3H), 7.18 (t, J¼7.6 Hz, 1H), 6.95–6.92 (m, 2H), 3.88 (s, 3H), 2.06–2.01
4H), 0.78 (t, J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 191.28,
(m, 2H), 1.44–1.35 (m, 2H), 1.28–1.19 (m, 2H), 0.81 (t, J¼7.2 Hz, 3H).
146.17, 144.66, 141.90, 136.83, 136.41, 134.46, 129.85, 129.74, 128.83,
128.43, 30.10, 29.53, 22.16, 21.69,13.61. MS (EI, 70 eV): m/z 342 (Mþ,
8.5), 177 (100), 119 (62), 91 (42). Anal. Calcd for C20H22SO3: C, 70.15;
H, 6.48. Found: C, 69.88; H, 6.23.
13C NMR (100 MHz, CDCl3):
d 189.22, 164.75, 146.09, 141.81, 139.91,
133.54, 132.43, 129.51, 129.03, 128.35, 114.12, 55.64, 30.16, 29.56,
22.20, 13.65. MS (EI, 70 eV): m/z 358 (Mþ, 5.4), 269 (100), 135 (34).
Anal. Calcd for C20H22SO4: C, 67.01; H, 6.19. Found: C, 66.73; H,
5.95.
4.3.3. (Z)-1-(4-Nitrobenzoyl)-1-phenylsulfonyl-1-hexene (4c)
Oil. IR (film):
n
(cmꢀ1) 3068, 2928, 1623, 1600, 1520, 1348, 1306,
4.3.9. (Z)-1-Benzoyl-1-phenylsulfonyl-2-phenylethene (4i)
1152, 847, 729. 1H NMR (400 MHz, CDCl3):
d
8.11 (d, J¼8.4 Hz, 2H),
White solid, 97–98 ꢁC. IR (KBr): (cmꢀ1) 1659, 1614, 1447, 1304,
n
7.66 (d, J¼7.6 Hz, 2H), 7.60–7.56 (m, 1H), 7.47–7.39 (m, 4H), 6.27 (t,
J¼7.6 Hz, 1H), 2.93–2.87 (m, 2H), 1.44–1.32 (m, 4H), 0.95 (t,
1230, 1141, 1085, 687. 1H NMR (400 MHz, CDCl3):
7.91–7.87 (m, 4H), 7.65–7.18 (m, 11H). 13C NMR (100 MHz, CDCl3):
192.20, 141.57, 139.72, 139.44, 135.45, 134.50, 133.75, 131.38,
d 8.06 (s, 1H),
J¼7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d
190.07, 148.93, 142.40,
d
140.54, 133.63, 131.09, 129.21, 129.11, 127.61, 127.25, 123.21, 31.28,
28.66, 22.45, 13.88. MS (EI, 70 eV): m/z 373 (Mþ, 4.1), 225 (100), 143
(39),116 (46). Anal. Calcd for C19H19NSO5: C, 61.11; H, 5.13. Found: C,
60.87; H, 4.92.
131.16, 130.30, 129.85, 129.13, 128.92, 128.82, 128.63. MS (EI, 70 eV):
m/z 348 (Mþ, 5.7), 207 (31), 177 (100), 105 (89), 77 (49). Anal. Calcd
for C21H16SO3: C, 72.39; H, 4.63. Found: C, 72.11; H, 4.40.
4.3.10. (Z)-1-(4-Chlorobenzoyl)-1-phenylsulfonyl-2-
4.3.4. (Z)-1-(4-Chlorobenzoyl)-1-(p-tolylsulfonyl)-1-hexene (4d)
phenylethene (4j)
Oil. IR (film):
733. 1H NMR (400 MHz, CDCl3):
J¼8.0 Hz, 2H), 7.45 (d, J¼8.4 Hz, 2H), 7.31 (d, J¼8.0 Hz, 2H), 7.19
n
(cmꢀ1) 2930, 1669, 1587, 1320, 1154, 1086, 911,
White solid, 108–109 ꢁC. IR (KBr):
n
(cmꢀ1) 2957, 1659, 1616,
8.06
(s, 1H), 7.89 (d, J¼8.4 Hz, 2H), 7.82 (d, J¼8.4 Hz, 2H), 7.67–7.52 (m,
d
7.84 (d, J¼8.8 Hz, 2H), 7.68 (d,
1582, 1307, 1228, 1146, 1086, 687. 1H NMR (400 MHz, CDCl3):
d

S. You et al. / Tetrahedron 65 (2009) 6863–6867
6867
3H), 7.34–7.22 (m, 7H). 13C NMR (100 MHz, CDCl3):
d
191.07, 141.77,
preparative TLC on silica gel to afford the corresponding
compounds.
141.18, 139.53, 139.06, 133.87, 133.83, 131.37, 131.20, 131.15, 130.22,
129.26, 129.19, 129.03, 128.62. MS (EI, 70 eV): m/z 382 (Mþ, 35Cl,
8.6), 185 (26), 177 (100), 120 (91). Anal. Calcd for C21H15SO3Cl: C,
65.87; H, 3.95. Found: C, 65.59; H, 3.77.
Acknowledgements
We thank the National Natural Science Foundation of China
(Project No. 20862008) and the Natural Science Foundation of
Jiangxi Province of China (2007GZW0172) for financial support.
4.3.11. (Z)-1-(4-Nitrobenzoyl)-1-phenylsulfonyl-2-
phenylethene (4k)
Yellow solid, 124–125 ꢁC. IR (KBr):
n
(cmꢀ1) 3059, 1669, 1605,
1529, 1345, 1150, 853. 1H NMR (400 MHz, CDCl3):
d 8.19 (d,
References and notes
J¼8.8 Hz, 2H), 7.61 (d, J¼8.8 Hz, 2H), 7.51–7.22 (m, 11H). 13C NMR
(100 MHz, CDCl3):
d 191.04, 143.08, 139.71, 133.46, 132.76, 130.89,
1. Nielsen, A. T.; Houlihan, W. Org. React. 1968, 16, 15.
2. Chong, B. D.;Ji, Y. I.; Oh, S. S.;Yang, J. D.;Baik, W.; Koo, S. J. Org. Chem.1997, 62, 9323.
3. Nenitzescu, C. D.; Balaban, A. T. In Friedel-Crafts and Related Reactions; Olah, G.
A. Ed.; Interscience: New York, NY, 1964; Vol. 3, p 1033.
130.69, 130.14, 129.48, 129.18, 128.73, 128.67, 128.05, 127.98, 123.44.
MS (EI, 70 eV): m/z 393 (Mþ, 3.4), 185 (100). Anal. Calcd for
C21H15NSO5: C, 64.11; H, 3.84. Found: C, 63.84; H, 3.65.
4. Carr, D. B.; Schwartz, J. J. Am. Chem. Soc. 1977, 99, 639.
5. Sung, J. W.; Jang, W. B.; Oh, D. Y. Tetrahedron Lett. 1996, 37, 7537.
6. Zhao, C. Q.; Huang, X. Tetrahedron Lett. 1998, 39, 1933.
7. Huang, Z. Z.; Huang, X.; Huang, Y. Z. J. Chem. Soc., Perkin Trans. 1 1995, 95.
8. Ma, Y.; Li, B.; Huang, X. J. Organomet. Chem. 1999, 590, 234.
9. Monteiro, H. J.; Gemal, A. L. Synthesis 1975, 437.
10. Durman, J.; Grayson, J. I.; Hunt, P. G.; Warren, S. J. Chem. Soc., Perkin Trans. 1
1986, 1939.
11. Yechezkel, T.; Ghera, E.; Ostercamp, D.; Hassner, A. J. Org. Chem. 1995, 60, 5135.
12. Fringuell, F.; Pizzo, F.; Vaccaro, L. J. Org. Chem. 2004, 69, 2315.
13. Xu, F.; Shi, W.; Wang, J. J. Org. Chem. 2005, 70, 4191.
14. Bernard, A. M.; Frongia, A.; Pier, P. P.; Secci, F.; Spiga, M. Org. Lett. 2005, 7, 4565.
15. Palasz, A. Org. Biomol. Chem. 2005, 3, 3207.
16. Cao, W.; Ding, W.; Chen, J.; Chen, Y.; Zang, Q.; Chen, G. Synth. Commun. 2004, 34,1599.
17. Cao, W.; Zhang, H.; Chen, J.; Zhou, X.; Shao, M.; McMills, M. C. Tetrahedron 2008,
64, 163.
4.3.12. (Z)-1-(4-Methylbenzoyl)-1-phenylsulfonyl-2-
phenylethene (4l)
White solid, 95–96 ꢁC. IR (KBr):
n
(cmꢀ1) 1654, 1615, 1449,
8.02 (s,
1306, 1232, 1145, 1087, 689. 1H NMR (400 MHz, CDCl3):
d
1H), 7.90–7.88 (m, 2H), 7.79 (d, J¼8.4 Hz, 2H), 7.63–7.51 (m, 3H),
7.30–7.19 (m, 5H), 7.16 (d, J¼8.0 Hz, 2H), 2.35 (s, 3H). 13C NMR
(100 MHz, CDCl3):
d 191.67, 145.78, 141.17, 139.74, 139.59, 133.69,
133.12, 131.47, 131.07, 130.31, 130.05, 129.60, 129.10, 128.90,
128.60, 21.84. MS (EI, 70 eV): m/z 362 (Mþ, 2.1), 119 (100), 91 (78),
77 (38). Anal. Calcd for C22H18SO3: C, 72.90; H, 5.01. Found: C,
72.63; H, 4.86.
18. Monteiro, N.; Balme, G. J. Org. Chem. 2000, 65, 3223.
19. Swenson, R. E.; Sowin, T. J.; Zhang, H. Q. J. Org. Chem. 2002, 67, 9182.
20. Chodroff, S.; Whitmore, W. F. J. Am. Chem. Soc. 1950, 72, 1073.
21. Balasubramanian, M.; Baliah, V. J. Indian Chem. Soc. 1955, 32, 493.
22. Villemin, D.; Ben Alloum, A. Synth. Commun. 1991, 21, 63.
23. Padwa, A.; Chiacchio, U.; Kline, D. N.; Perumattam, J. J. Org. Chem. 1988, 53, 2238.
24. Caturla, F.; Najera, C. Tetrahedron 1997, 53, 11449.
4.4. General procedure for one-pot stereoselective synthesis
of (Z)-
a-arylsulfonyl-a,b-unsaturated ketones
25. Thibonnet, J.; Anh Vu, V.; Berillon, L.; Knochel, P. Tetrahedron 2002, 58, 4787.
26. Trost, B. M.; Li, C. J. Synthesis 1994, 1267.
27. Magriotis, P. A.; Brown, J. T.; Scott, M. E. Tetrahedron Lett. 1991, 32, 5047.
28. Paley, R. S.; Weers, H. L.; Fernandez, P. Tetrahedron Lett. 1995, 36, 3605.
29. Huang, X.; Ma, Y. Synth. Commun. 1997, 27, 2407.
30. Xiang, J. S.; Mahadevan, A.; Fuches, P. L. J. Am. Chem. Soc. 1996, 118, 4284.
31. Leusink, A. J.; Budding, H. A.; Marsman, J. W. J. Organomet. Chem. 1967, 9, 285.
32. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
33. Tietze, L. F.; Beifuss, U. Angew. Chem., Int. Ed. Engl. 1993, 32, 131.
34. Bunce, R. A. Tetrahedron 1995, 48, 13103.
A
25 mL, two-necked, round-bottom flask equipped with
a magnetic stirring bar under argon atmosphere, was charged se-
quentially with acetylenic sulfone (1 mmol), benzene (3 mL),
Pd(PPh3)4 (0.05 mmol) and Bu3SnH (1.05 mmol). The mixture was
stirred at room temperature for 2 h. Then acyl chloride (1.1 mmol)
and CuI (0.75 mmol) were added and the mixture was stirred at
reflux for 7–10 h, cooled to room temperature, and diluted with
light petroleum. The supernatant was filtered through a short plug
of silica gel and the filtrate evaporated. The residue was purified by
35. Tietze, L. F. Chem. Rev. 1996, 96, 115.
36. Huang, X.; Xie, M. H. Org. Lett. 2002, 4, 1331.