A one-pot, stereoselective synthesis of 1,3- and 1,4-dienyl sulfones by hydrostannylation-Stille tandem reaction of tributyltin hydride with acetylenic sulfones and alkenyl or allylic halides

Article abstract of DOI:10.1055/s-2007-965977

1,3-Dienyl and 1,4-dienyl sulfones can be stereoselectively synthesized in one pot under mild conditions, in good yields, by the palladium-catalyzed hydrostannylation of acetylenic sulfones, followed by Stille coupling with alkenyl or allylic halides, res

Full text of DOI:10.1055/s-2007-965977

PAPER
1197
A One-Pot, Stereoselective Synthesis of 1,3- and 1,4-Dienyl Sulfones by
Hydrostannylation–Stille Tandem Reaction of Tributyltin Hydride with
Acetylenic Sulfones and Alkenyl or Allylic Halides
O
ne-Pot, Stereoselectiv
i
e
Synt
n
hesis of 1,3-
g
and 1,4-Dien
z
yl Sulfoneshong Cai,* Guiqin Chen, Wenyan Hao
School of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. of China
Fax +86(791)8120388; E-mail: caimzhong@163.com
Received 9 January 2007; revised 13 February 2007
termediates in organic synthesis17 due to the chemical ver-
satility of the sulfone moiety, which can be prepared by
oxidation of the corresponding 1,3-dienyl sulfides.18
However, reports on the stereocontrolled synthesis of 1,3-
dienyl sulfones are limited19 and the synthesis of 1,4-di-
enyl sulfones has received even less attention.20 The tan-
dem reaction has recently been of interest for organic
synthesis because it offers a convenient and economical
method with which to prepare target organic molecules.21
The palladium-catalyzed hydrostannylation of alkynes
and the Stille reaction are acknowledged as useful tools
for constructing complex organic molecules, however,
there have been no reports on the palladium-catalyzed tan-
dem hydrostannylation–Stille reaction of tributyltin hy-
dride (Bu3SnH) with alkynes and organic halides to date.
Herein we wish to report that 1,3- and 1,4-dienyl sulfones
can be stereoselectively synthesized in one pot, under
mild conditions, in good yields by the palladium-cata-
lyzed hydrostannylation of acetylenic sulfones, followed
by Stille coupling with alkenyl or allylic halides, respec-
tively.
Abstract: 1,3-Dienyl and 1,4-dienyl sulfones can be stereoselec-
tively synthesized in one pot under mild conditions, in good yields,
by the palladium-catalyzed hydrostannylation of acetylenic sul-
fones, followed by Stille coupling with alkenyl or allylic halides, re-
spectively.
Key words: acetylenic sulfone, hydrostannylation, Stille coupling,
1,3-dienyl sulfone, 1,4-dienyl sulfone
The stereocontrolled synthesis of conjugated dienes has
attracted considerable interest in organic chemistry be-
cause of their appearance in a wide variety of biologically
active molecules and as key synthetic intermediates.1
Conjugated dienes are usually prepared by utilizing either
a Wittig-type approach2 or through transition-metal-cata-
lyzed coupling reactions of stereodefined vinyl halides
with vinyl organometallic compounds.3 Recently, Whitby
and co-workers reported the insertion of 1-lithio-1-halo-
butadiene into organozirconocenes, providing a stereo-
controlled synthesis of (E,Z)-1,3-dienes.4 The 1,4-diene
framework also constitutes an important structural assem-
bly in many molecules of biological importance5 in addi-
tion to its application in organic synthesis6 so, for these
reasons, the synthesis of 1,4-dienes has also attracted
much interest.7 Many methods can be used for the stereo-
controlled synthesis of 1,4-dienes.8 Very recently, Kabal-
ka et al. reported a new route to 1,4-pentadienes via
microwave-enhanced palladium-catalyzed cross-coupling
reactions of potassium vinyltrifluoroborates and allyl ace-
tates.9
Palladium-catalyzed hydrostannylation of alkynes pro-
vides a simple, general route for the synthesis of vinyl-
stannanes.22 In 1991, Magriotis reported that the
palladium-catalyzed hydrostannylation of phenylthio-
alkynes with tributyltin hydride was highly regio- and ste-
reoselective, giving (E)-a-stannylvinyl sulfides in high
yields.23 Paley et al. reported that the palladium-catalyzed
hydrostannylation of chiral alkynyl sulfoxides at –78 °C
was also highly regio- and stereoselective, affording
chiral (E)-a-stannylvinyl sulfoxides in good yields.24
Huang and Ma demonstrated that alkynyl selenides can
also undergo palladium-catalyzed hydrostannylation to
stereoselectively afford (E)-a-stannylvinyl selenides.25
Xiang et al. reported that palladium-catalyzed hydrostan-
nylation of acetylenic triflones with tributyltin hydride
provided a-stannylated vinyl triflones regiospecifically,
however the reaction was not stereospecific and afforded
a 1:1.7 ratio of E and Z stereoisomers.26 Recently, we have
found that the palladium-catalyzed hydrostannylation of
acetylenic sulfones can proceed highly regio- and stereo-
selectively, affording (E)-a-stannylvinyl sulfones in high
yields.27 (E)-a-Stannylvinyl sulfones are new difunctional
group reagents in which two synthetically versatile groups
are linked to the same olefinic carbon atom and can be
considered both as vinylstannanes and as vinyl sulfones.
The stereocontrolled synthesis of 1,3- and 1,4-dienes con-
taining metal or heteroatom functional groups is also of
considerable interest in organic synthesis because many
useful functional group transformations can be achieved
through the introduction and removal of such groups. Het-
eroatom-substituted 1,3-dienes are also useful precursors
for the construction of highly functionalized ring systems
in Diels–Alder reactions.10 The stereoselective synthesis
of 1,3-dienyl silanes,11 1,4-dienyl silanes,12 1,3-dienyl sul-
fides,13 1,3-dienyl selenides,14 1,4-dienyl selenides15 and
1,3-dienyl stannanes16 have already been described in the
literature. 1,3-Dienyl sulfones are extensively used as in-
SYNTHESIS 2007, No. 8, pp 1197–1203
x
x
.
x
x
.2
0
0
7
Advanced online publication: 23.03.2007
DOI: 10.1055/s-2007-965977; Art ID: F00307SS
© Georg Thieme Verlag Stuttgart · New York

1198
M. Cai et al.
PAPER
Table 1 Synthesis of (Z,E)-2-Arylsulfonyl-Substituted 1,3-Dienes
3
Vinylstannanes can undergo the Stille coupling reaction
with organic halides.28 Considering the fact that both the
hydrostannylation and Stille reactions were catalyzed by
tetrakis(triphenylphosphine)palladium [Pd(PPh3)4], we
tried to combine the two reactions, in one pot, to stereo-
selectively prepare 1,3-dienyl sulfones (Scheme 1).
R
Ar
R1
Product Yielda (%)
n-Bu
4-MeC6H4
n-Bu
Ph
3a
3b
3c
3d
3e
3f
72
81
75
69
67
65
77
83
66
70
75
73
71
69
n-Bu
Ph
We found that, hydrostannylation of acetylenic sulfones 1
with tributyltin hydride using 5 mol% Pd(PPh3)4 in ben-
zene, followed by solvent exchange (to DMF) and subse-
quent reaction with alkenyl iodides and 75 mol% copper
iodide, gave the (Z,E)-2-arylsulfonyl-substituted 1,3-
dienes 3 in good yields. As can be seen from the experi-
mental results summarized in Table 1, the tandem hy-
drostannylation–Stille reaction of tributyltin hydride with
a variety of acetylenic sulfones and alkenyl iodides pro-
ceeded smoothly, under very mild conditions, to afford
the corresponding (Z,E)-2-arylsulfonyl-substituted 1,3-
dienes 3 stereoselectively. The Stille coupling reaction of
the intermediates 2 with alkenyl bromides was very slow
under the same reaction conditions, with only traces of
coupling products obtained after 24 hours of reaction
time. The Stille coupling reaction of the intermediates 2
with alkenyl chlorides did not occur at all.
n-Bu
4-MeC6H4
Ph
n-Bu
4-MeC6H4
MeOCH2
MeOCH2
MeOCH2
Ph
n-Bu
Ph
Ph
Ph
Ph
Ph
3g
3h
3i
Ph
Ph
n-Bu
MeOCH2
Ph
MeOCH2
MeOCH2
MeOCH2
MeOCH2
MeOCH2
n-Bu
Ph
Ph
3j
4-MeC6H4
4-MeC6H4
Ph
Ph
3k
3l
n-Bu
n-Bu
n-Bu
3m
3n
We have also investigated a one-pot, stereoselective syn-
thesis of 1,4-dienyl sulfones by the tandem hydrostan-
nylation–Stille reaction of tributyltin hydride with
acetylenic sulfones and allylic bromides (Scheme 2). We
observed that, after the hydrostannylation reaction of ace-
tylenic sulfones 1 and subsequent reaction of the inter-
mediate 2 with allylic bromides and copper iodide, in the
manner described above, the desired (Z)-2-arylsulfonyl-
substituted 1,4-dienes 4 were obtained in good yields. The
experimental results (summarized in Table 2) show that
the tandem hydrostannylation–Stille reaction of tributyl-
tin hydride with a variety of acetylenic sulfones and allyl-
ic bromides also proceeded smoothly, under very mild
conditions, to give the corresponding (Z)-2-arylsulfonyl-
substituted 1,4-dienes 4 stereoselectively. When allylic
bromides were replaced by allylic chlorides, no Stille re-
action was observed.
Ph
a Isolated yield based on the alkenyl iodide used.
palladium catalyst, occurs with retention of configura-
tion.29 The (1E)-configuration of compounds 3a–i and
1
3l–n has been shown by their H NMR spectra, which
show a doublet at d = 6.02–7.17 ppm with a coupling con-
stant of 15.2–16.2 Hz; this is also evidence of the retention
of the E-configuration of the starting alkenyl iodides. In
addition, the (3Z)-configuration of compound 3d was con-
firmed by NOESY experiments. An enhancement of the
allylic protons was observed as the vinylic proton
(d = 6.28 ppm) of 3d was irradiated. There was no corre-
lation between the vinylic proton (d = 6.28 ppm) and the
aromatic protons. A correlation between the vinylic pro-
ton (d = 6.28 ppm) and one other vinylic proton (d = 6.40
ppm) was also observed. The NOE results indicate that 3d
has the expected (1E,3Z)-configuration and that the cross-
It is well documented that the Stille coupling reaction of
vinylstannanes with organic halides, in the presence of a
H
I
R
H
SO2Ar
R
SO2Ar
SnBu3
H
Bu3SnH, Pd(PPh3)4
R1
R
SO2Ar
H
benzene, r.t.
R1
H
CuI, DMF, r.t., 5–7 h
H
1
3
2
Scheme 1
R2
R1
H
R
H
SO2Ar
R2
R
H
SO2Ar
SnBu3
Br
Bu3SnH, Pd(PPh3)4
benzene, r.t.
R
SO2Ar
R1
CuI, DMF, r.t., 8 h
1
4
2
H
Scheme 2
Synthesis 2007, No. 8, 1197–1203 © Thieme Stuttgart · New York

PAPER
One-Pot, Stereoselective Synthesis of 1,3- and 1,4-Dienyl Sulfones
1199
(Z,E)-2-Arylsulfonyl-Substituted 1,3-Dienes 3a–n; General
Procedure
Table 2 Synthesis of (Z)-2-Arylsulfonyl-Substituted 1,4-Dienes 4
R
Ar
R1
H
R2
H
Product Yielda (%)
A 25 mL, two-necked, round-bottom flask equipped with a magnet-
ic stirring bar under an argon atmosphere, was charged sequentially
with acetylenic sulfone 1 (1 mmol), benzene (4 mL), Pd(PPh3)4
(0.05 mmol) and Bu3SnH (1.05 mmol). The mixture was stirred at
r.t. for 4 h then the solvent was removed under reduced pressure and
the residue was dissolved in DMF (10 mL). Alkenyl iodide (0.9
mmol) and CuI (0.7 mmol) were added and the mixture was stirred
at r.t. for 5–7 h. The reaction mixture was diluted with Et2O (30
mL), filtered and then treated with 20% aqueous KF (10 mL) for 30
min before the organic layer was taken, dried (MgSO4) and concen-
trated. The residue was purified by column chromatography on sil-
ica gel (PE–Et2O, 5:1).
n-Bu
n-Bu
Ph
4a
4b
4c
4d
4e
4f
78
74
70
76
75
72
69
77
81
4-MeC6H4
H
H
MeOCH2 Ph
H
H
Ph
Ph
Ph
Ph
H
H
n-Bu
Ph
Ph
Ph
Ph
H
H
H
MeOCH2 4-MeC6H4
H
4g
4h
4i
(5Z,7E)-6-(4-Methylphenyl)sulfonyl-5,7-dodecadiene (3a)
Colorless liquid.
n-Bu
Ph
Ph
Me
Me
IR (film): 3030, 2957, 2928, 1715, 1620, 1598, 1457, 1321, 1155,
1086, 966, 813, 678 cm–1.
1H NMR (CDCl3): d = 7.73 (d, J = 8.4 Hz, 2 H), 7.29 (d, J = 8.4 Hz,
2 H), 6.16 (t, J = 7.6 Hz, 1 H), 6.14 (d, J = 15.2 Hz, 1 H), 5.77 (dt,
J = 15.2, 7.6 Hz, 1 H), 2.69–2.61 (m, 2 H), 2.42 (s, 3 H), 2.09–2.02
(m, 2 H), 1.39–1.22 (m, 8 H), 0.92–0.85 (m, 6 H).
Ph
H
a Isolated yield based on the allylic bromide used.
coupling reaction of (E)-a-stannylvinyl sulfones with alk-
enyl iodides occurs with retention of configuration of both
the starting compounds 2 and the alkenyl iodides. The
(4E)-configuration of the compounds 4e–g was demon-
strated by their 1H NMR spectra, which show a doublet at
d = 6.53–6.32 ppm with a coupling constant of 15.6–16.0
Hz. In addition, the (1Z)-configuration of compound 4h
was confirmed by NOESY experiments. An enhancement
of the allylic protons was observed as the vinylic proton
(d = 6.03 ppm) of 4h was irradiated. There was no corre-
lation between the vinylic proton (d = 6.03 ppm) and the
aromatic protons. A correlation between the vinylic pro-
ton (d = 6.03 ppm) and the allylic protons (d = 3.03 ppm)
was also observed. The NOE results indicate that 4h has
the expected (1Z)-configuration and that the cross-cou-
pling reaction of (E)-a-stannylvinyl sulfones with allylic
bromides occurs with retention of configuration.
13C NMR (CDCl3): d = 143.9, 141.8, 140.2, 138.7, 136.3, 129.5,
127.4, 124.5, 32.5, 31.4, 31.0, 28.3, 22.4, 22.1, 21.6, 13.9.
MS: m/z (%) = 320 (2.4) [M+], 91 (34), 79 (43), 67 (97), 55 (82), 41
(100).
Anal. Calcd for C19H28SO2: C, 71.25; H, 8.74. Found: C, 71.03; H,
8.62.
(1E,3Z)-1-Phenyl-3-phenylsulfonyl-1,3-octadiene (3b)
Colorless liquid.
IR (film): 3060, 2958, 2929, 1716, 1623, 1585, 1494, 1447, 1305,
1153, 1085, 963, 731, 689 cm–1.
1H NMR (CDCl3): d = 7.89 (d, J = 8.0 Hz, 2 H), 7.59–7.26 (m,
8 H), 6.93 (d, J = 16.0 Hz, 1 H), 6.69 (d, J = 16.0 Hz, 1 H), 6.43 (t,
J = 8.0 Hz, 1 H), 2.76–2.70 (m, 2 H), 1.46–1.32 (m, 4 H), 0.91 (t,
J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 143.1, 141.6, 140.1, 136.3, 133.2, 132.9,
129.1, 128.7, 128.4, 127.2, 126.9, 123.0, 31.4, 28.7, 22.4, 13.9.
In conclusion, we have developed an efficient and stereo-
selective one-pot method for the synthesis of 1,3- and 1,4-
dienyl sulfones. The present method has the advantages of
readily available starting materials, straightforward and
simple procedures, mild reaction conditions and good
yields. The procedure should find wide application in the
synthesis of a large array of naturally occurring sub-
stances having a 1,3- or 1,4-diene system.
MS: m/z (%) = 326 (2.7) [M+], 185 (9), 155 (13), 143 (17), 129 (34),
77 (28), 57 (35), 41 (100).
Anal. Calcd for C20H22SO2: C, 73.62; H, 6.74. Found: C, 73.35; H,
6.53.
(1E,3Z)-1-Phenyl-3-(4-methylphenyl)sulfonyl-1,3-octadiene
(3c)
Colorless liquid.
IR (film): 3059, 2957, 2928, 1714, 1622, 1597, 1495, 1449, 1291,
1151, 1086, 963, 813, 693 cm–1.
1H NMR (CDCl3): d = 7.77 (d, J = 8.0 Hz, 2 H), 7.41–7.26 (m,
7 H), 6.93 (d, J = 15.6 Hz, 1 H), 6.68 (d, J = 15.6 Hz, 1 H), 6.40 (t,
J = 7.6 Hz, 1 H), 2.76–2.70 (m, 2 H), 2.41 (s, 3 H), 1.46–1.33 (m,
4 H), 0.92 (t, J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 144.2, 142.7, 140.3, 138.7, 136.4, 132.8,
129.7, 128.7, 128.4, 127.3, 126.9, 123.1, 31.4, 28.7, 22.5, 21.6,
13.9.
1H NMR spectra were recorded on a Bruker AC-P400 (400 MHz)
spectrometer with TMS as an internal standard using CDCl3 as the
solvent. 13C NMR (100 MHz) spectra were recorded on a Bruker
AC-P400 (400 MHz) spectrometer using CDCl3 as the solvent. IR
spectra were determined on an FTS-185 instrument as neat films.
Mass spectra were obtained on a Finigan 8239 mass spectrometer
(EI, 70 eV). Microanalyses were measured using a Yanaco MT-3
CHN microelemental analyzer. All reactions were carried out in
pre-dried glassware (150 °C, 4 h) and cooled under a stream of dry
Ar. Benzene was distilled from sodium prior to use. DMF was dried
by distillation over calcium hydride. Light petroleum ether (PE)
used for column chromatograph had a boiling range of 30–60 °C.
MS: m/z (%) = 340 (3.8) [M+], 185 (14), 155 (21), 143 (27), 129
(63), 91 (100).
Anal. Calcd for C21H24SO2: C, 74.12; H, 7.05. Found: C, 73.87; H,
7.08.
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1200
M. Cai et al.
PAPER
(2E,4Z)-1-Methoxy-4-(4-methylphenyl)sulfonyl-2,4-nonadiene
(3d)
IR (film): 3060, 3027, 1718, 1621, 1585, 1491, 1292, 1159, 1091,
964, 748, 687 cm–1.
Colorless liquid.
1H NMR (CDCl3): d = 7.65 (d, J = 7.6 Hz, 2 H), 7.47–7.24 (m,
14 H), 7.17 (d, J = 15.6 Hz, 1 H), 6.94 (d, J = 15.6 Hz, 1 H).
13C NMR (CDCl3): d = 142.1, 140.9, 136.8, 136.2, 134.4, 133.9,
133.0, 129.8, 128.9, 128.8, 128.7, 128.6, 127.8, 127.7, 127.1, 123.0.
IR (film): 2927, 2872, 1720, 1620, 1597, 1494, 1455, 1302, 1153,
1086, 966, 814, 679 cm–1.
1H NMR (CDCl3): d = 7.73 (d, J = 8.0 Hz, 2 H), 7.30 (d, J = 8.0 Hz,
2 H), 6.40 (d, J = 15.8 Hz, 1 H), 6.28 (t, J = 7.6 Hz, 1 H), 5.92 (dt,
J = 15.8, 5.8 Hz, 1 H), 3.94 (d, J = 5.6 Hz, 2 H), 3.29 (s, 3 H), 2.71–
2.65 (m, 2 H), 2.42 (s, 3 H), 1.41–1.26 (m, 4 H), 0.89 (t, J = 7.2 Hz,
3 H).
MS: m/z (%) = 346 (16) [M+], 205 (100), 77 (43).
Anal. Calcd for C22H18SO2: C, 76.30; H, 5.20. Found: C, 76.11; H,
5.03.
13C NMR (CDCl3): d = 144.1, 143.6, 139.5, 138.6, 130.7, 129.6,
127.3, 126.9, 72.4, 58.1, 31.3, 28.4, 22.4, 21.6, 13.8. For NOESY
correlations, see Figure 1.
MS: m/z (%) = 308 (1.1) [M+], 139 (16), 110 (100), 91 (37), 45 (23),
41 (14).
(1Z,3E)-1-Phenyl-2-phenylsulfonyl-1,3-octadiene (3h)
Colorless liquid.
IR (film): 3059, 2956, 2928, 1714, 1634, 1586, 1446, 1305, 1150,
1082, 966, 750, 688 cm–1.
1H NMR (CDCl3): d = 7.62 (d, J = 7.6 Hz, 2 H), 7.49–7.26 (m,
8 H), 7.18 (s, 1 H), 6.38 (d, J = 15.4 Hz, 1 H), 6.08 (dt, J = 15.4, 7.2
Hz, 1 H), 2.19–2.14 (m, 2 H), 1.42–1.25 (m, 4 H), 0.92 (t, J = 7.6
Hz, 3 H).
Anal. Calcd for C17H24SO3: C, 66.24; H, 7.79. Found: C, 66.13; H,
7.53.
CH3
13C NMR (CDCl3): d = 142.1, 140.8, 138.2, 136.3, 134.0, 132.9,
129.6, 128.5, 128.4, 127.7, 124.4, 32.7, 31.0, 22.2, 13.9.
observed NOESY correlations
H
MS: m/z (%) = 326 (4.8) [M+], 184 (26), 155 (57), 128 (67), 115
(88), 91 (100), 77 (63), 41 (78).
H
vinyl / CH2(allylic)
CH3(CH2)2CH2
H
SO2
CH2(allylic) / CH(aromatic)
Hvinyl / Hvinyl
H
Anal. Calcd for C20H22SO2: C, 73.62; H, 6.74. Found: C, 73.48; H,
6.49.
H
CH2OCH3
3d
(2Z,4E)-1,6-Dimethoxy-3-phenylsulfonyl-2,4-hexadiene (3i)
Colorless liquid.
Figure 1
IR (film): 3064, 2929, 2824, 1721, 1628, 1584, 1447, 1306, 1153,
962, 734, 689 cm–1.
1H NMR (CDCl3): d = 7.86–7.84 (m, 2 H), 7.63–7.52 (m, 3 H), 6.40
(t, J = 5.2 Hz, 1 H), 6.27 (d, J = 15.6 Hz, 1 H), 6.02 (dt, J = 15.6, 5.6
Hz, 1 H), 4.65 (d, J = 5.2 Hz, 2 H), 3.92 (d, J = 5.2 Hz, 2 H), 3.39
(s, 3 H), 3.25 (s, 3 H).
13C NMR (CDCl3): d = 141.0, 140.3, 138.5, 133.7, 132.3, 129.2,
127.4, 124.8, 72.1, 69.5, 58.7, 58.1.
MS: m/z (%) = 282 (2.8) [M+], 141 (29), 125 (61), 109 (79), 77 (67),
45 (100).
(2E,4Z)-1-Methoxy-4-phenylsulfonyl-2,4-nonadiene (3e)
Colorless liquid.
IR (film): 3065, 2957, 2929, 1717, 1618, 1584, 1447, 1306, 1155,
1086, 965, 728, 689 cm–1.
1H NMR (CDCl3): d = 7.87–7.85 (m, 2 H), 7.60–7.50 (m, 3 H), 6.42
(d, J = 15.6 Hz, 1 H), 6.32 (t, J = 7.6 Hz, 1 H), 5.93 (dt, J = 15.6, 5.8
Hz, 1 H), 3.94 (d, J = 5.6 Hz, 2 H), 3.29 (s, 3 H), 2.72–2.63 (m,
2 H), 1.41–1.30 (m, 4 H), 0.89 (t, J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 144.1, 141.5, 139.2, 133.2, 130.8, 129.1,
127.2, 126.7, 72.4, 58.1, 31.2, 28.5, 22.4, 13.9.
Anal. Calcd for C14H18SO4: C, 59.58; H, 6.38. Found: C, 59.31; H,
6.20.
MS: m/z (%) = 294 (1.2) [M+], 121 (24), 110 (100), 105 (29), 79
(53), 45 (27), 41 (30).
Anal. Calcd for C16H22SO3: C, 65.31; H, 7.48. Found: C, 65.14; H,
7.25.
(1E,3Z)-1-Phenyl-3-phenylsulfonyl-5-methoxy-1,3-pentadiene
(3j)
Colorless liquid.
(1Z,3E)-1-Phenyl-2-phenylsulfonyl-5-methoxy-1,3-pentadiene
(3f)
Colorless liquid.
IR (film): 3062, 2941, 1613, 1582, 1447, 1369, 1302, 1151, 950,
740, 684 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 7.6 Hz, 2 H), 7.63–7.50 (m,
3 H), 7.38–7.26 (m, 5 H), 6.79 (s, 2 H), 6.52 (t, J = 5.2 Hz, 1 H),
4.68 (d, J = 5.2 Hz, 2 H), 3.42 (s, 3 H).
13C NMR (CDCl3): d = 140.5, 139.9, 139.5, 136.0, 134.3, 133.6,
129.2, 128.8, 128.7, 127.4, 126.9, 121.5, 69.6, 58.7.
IR (film): 3059, 2924, 2855, 1590, 1447, 1306, 1146, 1095, 970,
784, 744 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 8.0 Hz, 2 H), 7.58–7.38 (m,
9 H), 6.40 (dt, J = 16.2, 4.8 Hz, 1 H), 6.29 (d, J = 16.2 Hz, 1 H),
3.93 (d, J = 4.4 Hz, 2 H), 3.21 (s, 3 H).
13C NMR (CDCl3): d = 140.0, 138.3, 137.5, 136.0, 133.4, 133.1,
130.4, 129.9, 129.0, 128.7, 128.0, 120.2, 72.4, 58.1.
MS: m/z (%) = 314 (1.5) [M+], 157 (21), 141 (35), 129 (47), 115
(33), 77 (56), 45 (100).
Anal. Calcd for C18H18SO3: C, 68.80; H, 5.73. Found: C, 68.53; H,
5.64.
MS: m/z (%) = 314 (1.5) [M+], 204 (24), 185 (29), 155 (29), 143
(47), 129 (100), 115 (54), 91 (84), 77 (26).
Anal. Calcd for C18H18SO3: C, 68.80; H, 5.73. Found: C, 68.64; H,
5.50.
(1E,3Z)-1-Phenyl-3-(4-methylphenyl)sulfonyl-5-methoxy-1,3-
pentadiene (3k)
Colorless liquid.
(1Z,3E)-1,4-Diphenyl-2-phenylsulfonyl-1,3-butadiene (3g)
Colorless liquid.
IR (film): 3061, 2927, 1611, 1596, 1448, 1369, 1303, 1151, 947,
813, 740, 694 cm–1.
Synthesis 2007, No. 8, 1197–1203 © Thieme Stuttgart · New York

PAPER
One-Pot, Stereoselective Synthesis of 1,3- and 1,4-Dienyl Sulfones
1201
1H NMR (CDCl3): d = 7.76 (d, J = 8.0 Hz, 2 H), 7.38–7.26 (m,
7 H), 6.79 (s, 2 H), 6.49 (t, J = 5.2 Hz, 1 H), 4.68 (d, J = 4.8 Hz,
2 H), 3.42 (s, 3 H), 2.42 (s, 3 H).
13C NMR (CDCl3): d = 144.7, 139.7, 139.4, 137.5, 136.0, 134.1,
129.9, 128.8, 128.7, 127.4, 126.9, 121.6, 69.7, 58.7, 21.7.
MS: m/z (%) = 328 (3.3) [M+], 185 (15), 157 (25), 141 (73), 129
(100), 115 (56), 91 (87), 45 (66), 41 (25).
(Z)-2-Arylsulfonyl-Substituted 1,4-Dienes 4a–i; General Proce-
dure
A 25 mL, two-necked, round-bottom flask equipped with a magnet-
ic stirring bar under an argon atmosphere, was charged sequentially
with acetylenic sulfone 1 (1 mmol), benzene (4 mL), Pd(PPh3)4
(0.05 mmol) and Bu3SnH (1.05 mmol). The mixture was stirred at
r.t. for 4 h then the solvent was removed under reduced pressure and
the residue was dissolved in DMF (10 mL). Allylic bromide (0.9
mmol) and CuI (0.7 mmol) were added and the mixture was stirred
at r.t. for 8 h. The reaction mixture was diluted with Et2O (30 mL),
filtered and then treated with 20% aqueous KF (10 mL) for 30 min
before the organic layer was taken, dried (MgSO4) and concentrat-
ed. The residue was purified by column chromatography on silica
gel (PE–Et2O, 5:1).
Anal. Calcd for C19H20SO3: C, 69.52; H, 6.09. Found: C, 69.31; H,
5.85.
(2Z,4E)-1-Methoxy-3-(4-methylphenyl)sulfonyl-2,4-nonadiene
(3l)
Colorless liquid.
IR (film): 3030, 2927, 2873, 1718, 1640, 1598, 1494, 1454, 1302,
1152, 967, 814, 679 cm–1.
(Z)-1-Butyl-2-phenylsulfonyl-1,4-pentadiene (4a)
Colorless liquid.
1H NMR (CDCl3): d = 7.72 (d, J = 8.0 Hz, 2 H), 7.32 (d, J = 8.0 Hz,
2 H), 6.26 (t, J = 5.2 Hz, 1 H), 6.02 (d, J = 15.4 Hz, 1 H), 5.89 (dt,
J = 15.4, 6.8 Hz, 1 H), 4.62 (d, J = 4.8 Hz, 2 H), 3.39 (s, 3 H), 2.44
(s, 3 H), 2.07–2.01 (m, 2 H), 1.31–1.16 (m, 4 H), 0.84 (t, J = 7.2 Hz,
3 H).
13C NMR (CDCl3): d = 144.5, 139.6, 138.5, 137.8, 137.5, 129.7,
127.5, 123.1, 69.5, 58.6, 32.5, 30.8, 22.0, 21.7, 13.9.
IR (film): 3067, 2958, 1716, 1640, 1584, 1447, 1305, 1154, 921,
744, 689 cm–1.
1H NMR (CDCl3): d = 7.90–7.87 (m, 2 H), 7.61–7.51 (m, 3 H), 6.03
(t, J = 7.6 Hz, 1 H), 5.73–5.63 (m, 1 H), 5.11–5.04 (m, 2 H), 3.08–
3.06 (m, 2 H), 2.68–2.60 (m, 2 H), 1.37–1.25 (m, 4 H), 0.88 (t,
J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 144.5, 141.5, 138.9, 134.3, 133.2, 129.1,
127.4, 118.0, 36.8, 31.3, 28.4, 22.3, 13.9.
MS: m/z (%) = 264 (6.7) [M+], 263 (17) [M+ – 1], 235 (28), 143
(49), 125 (68), 93 (47), 81 (88), 79 (100), 77 (94).
MS: m/z (%) = 308 (1.2) [M+], 153 (46), 123 (37), 109 (38), 91 (68),
79 (54), 45 (100), 41 (69).
Anal. Calcd for C17H24SO3: C, 66.24; H, 7.79. Found: C, 66.02; H,
7.66.
Anal. Calcd for C15H20SO2: C, 68.14; H, 7.63. Found: C, 67.86; H,
7.49.
(2Z,4E)-1-Methoxy-3-phenylsulfonyl-2,4-nonadiene (3m)
Colorless liquid.
(Z)-1-Butyl-2-(4-methylphenyl)sulfonyl-1,4-pentadiene (4b)
Colorless liquid.
IR (film): 3066, 2930, 2873, 1713, 1640, 1585, 1447, 1306, 1152,
967, 734, 689 cm–1.
IR (film): 2927, 1713, 1640, 1598, 1458, 1302, 1139, 920, 814, 677
cm–1.
1H NMR (CDCl3): d = 7.76 (d, J = 8.0 Hz, 2 H), 7.32 (d, J = 8.0 Hz,
2 H), 5.99 (t, J = 7.6 Hz, 1 H), 5.75–5.63 (m, 1 H), 5.10–5.03 (m,
2 H), 3.06–3.04 (m, 2 H), 2.68–2.61 (m, 2 H), 2.44 (s, 3 H), 1.37–
1.24 (m, 4 H), 0.89 (t, J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 144.1, 144.0, 139.1, 138.5, 134.4, 129.7,
127.5, 117.9, 36.8, 31.3, 28.3, 22.4, 21.6, 13.9.
MS: m/z (%) = 278 (12) [M+], 178 (29), 157 (43), 139 (40), 91
(100), 57 (35).
1H NMR (CDCl3): d = 7.85–7.83 (m, 2 H), 7.62–7.51 (m, 3 H), 6.29
(t, J = 5.2 Hz, 1 H), 6.02 (d, J = 15.2 Hz, 1 H), 5.90 (dt, J = 15.2, 6.8
Hz, 1 H), 4.63 (d, J = 4.8 Hz, 2 H), 3.39 (s, 3 H), 2.05–2.01 (m,
2 H), 1.31–1.25 (m, 2 H), 1.21–1.15 (m, 2 H), 0.84 (t, J = 7.2 Hz,
3 H).
13C NMR (CDCl3): d = 140.4, 139.4, 139.0, 138.0, 133.5, 129.1,
127.5, 123.0, 69.5, 58.6, 32.5, 30.8, 22.0, 13.8.
MS: m/z (%) = 294 (1.7) [M+], 269 (100), 267 (71), 213 (64), 153
(63), 109 (65), 79 (81), 57 (68), 41 (98).
Anal. Calcd for C16H22SO3: C, 65.31; H, 7.48. Found: C, 65.09; H,
7.32.
Anal. Calcd for C16H22SO2: C, 69.02; H, 7.97. Found: C, 68.79; H,
7.78.
(5Z,7E)-6-Phenylsulfonyl-5,7-dodecadiene (3n)
Colorless liquid.
(Z)-1-Methoxy-3-phenylsulfonyl-2,5-hexadiene (4c)
Colorless liquid.
IR (film): 3065, 2957, 2928, 1714, 1620, 1585, 1446, 1305, 1156,
1086, 966, 728, 688 cm–1.
1H NMR (CDCl3): d = 7.85 (d, J = 7.6 Hz, 2 H), 7.59–7.48 (m,
3 H), 6.19 (t, J = 7.6 Hz, 1 H), 6.15 (d, J = 15.4 Hz, 1 H), 5.79 (dt,
J = 15.4, 7.2 Hz, 1 H), 2.70–2.64 (m, 2 H), 2.09–2.03 (m, 2 H),
1.41–1.22 (m, 8 H), 0.94–0.86 (m, 6 H).
13C NMR (CDCl3): d = 142.2, 141.6, 140.0, 136.5, 133.0, 128.9,
127.3, 124.4, 32.4, 31.4, 31.0, 28.4, 22.4, 22.1, 13.9.
MS: m/z (%) = 306 (3.4) [M+], 294 (27), 183 (44), 122 (65), 95 (72),
77 (100).
IR (film): 2927, 1714, 1641, 1584, 1447, 1308, 1151, 922, 814, 746
cm–1.
1H NMR (CDCl3): d = 7.89–7.87 (m, 2 H), 7.65–7.54 (m, 3 H), 6.16
(t, J = 4.8 Hz, 1 H), 5.68–5.57 (m, 1 H), 5.11–5.02 (m, 2 H), 4.64–
4.62 (m, 2 H), 3.39 (s, 3 H), 2.98–2.96 (m, 2 H).
13C NMR (CDCl3): d = 141.5, 139.9, 138.5, 133.7, 133.1, 129.3,
127.7, 118.9, 69.6, 58.6, 35.9.
MS: m/z (%) = 252 (1.3) [M+], 141 (12), 125 (21), 111 (100), 95
(43), 77 (35).
Anal. Calcd for C13H16SO3: C, 61.88; H, 6.34. Found: C, 61.62; H,
6.25.
Anal. Calcd for C18H26SO2: C, 70.59; H, 8.49. Found: C, 70.31; H,
8.37.
Synthesis 2007, No. 8, 1197–1203 © Thieme Stuttgart · New York

1202
M. Cai et al.
PAPER
(Z)-1-Butyl-2-phenylsulfonyl-4-methyl-1,4-pentadiene (4h)
(Z)-1-Phenyl-2-phenylsulfonyl-1,4-pentadiene (4d)
Colorless liquid.
Colorless liquid.
IR (film): 3063, 2956, 1714, 1640, 1585, 1446, 1305, 1148, 922,
748, 689 cm–1.
IR (film): 3077, 2929, 1715, 1652, 1585, 1446, 1305, 1152, 896,
724, 689 cm–1.
1H NMR (CDCl3): d = 7.55–7.43 (m, 3 H), 7.32–7.15 (m, 7 H), 7.04
(s, 1 H), 5.96–5.86 (m, 1 H), 5.26–5.21 (m, 2 H), 3.34–3.32 (m,
2 H).
13C NMR (CDCl3): d = 142.5, 140.4, 139.4, 134.0, 133.9, 132.9,
128.9, 128.5, 128.2, 127.8, 127.7, 118.8, 37.1.
MS: m/z (%) = 284 (32) [M+], 269 (63), 142 (100), 141 (86), 97
(58).
1H NMR (CDCl3): d = 7.90–7.87 (m, 2 H), 7.62–7.50 (m, 3 H), 6.03
(t, J = 7.6 Hz, 1 H), 4.86 (s, 1 H), 4.76 (s, 1 H), 3.03 (s, 2 H), 2.69–
2.62 (m, 2 H), 1.56 (s, 3 H), 1.37–1.25 (m, 4 H), 0.88 (t, J = 7.2 Hz,
3 H).
13C NMR (CDCl3): d = 144.9, 141.5, 141.4, 138.0, 133.1, 129.0,
127.5, 114.5, 40.9, 31.3, 28.4, 22.4, 21.4, 13.9. For NOESY corre-
lations, see Figure 2.
MS: m/z (%) = 279 (15) [M + H+], 278 (4.2) [M+], 137 (100), 121
(37), 95 (68), 81 (67), 79 (44), 77 (38).
Anal. Calcd for C17H16SO2: C, 71.80; H, 5.67. Found: C, 71.57; H,
5.49.
Anal. Calcd for C16H22SO2: C, 69.02; H, 7.97. Found: C, 68.87; H,
7.84.
(1Z,4E)-1-Butyl-2-phenylsulfonyl-5-phenyl-1,4-pentadiene (4e)
Colorless liquid.
IR (film): 3067, 2957, 1635, 1599, 1447, 1305, 1151, 967, 729, 690
cm–1.
1H NMR (CDCl3): d = 7.92–7.89 (m, 2 H), 7.60–7.49 (m, 3 H),
7.30–7.19 (m, 5 H), 6.38 (d, J = 15.6 Hz, 1 H), 6.12–5.98 (m, 2 H),
3.24 (d, J = 6.8 Hz, 2 H), 2.69–2.62 (m, 2 H), 1.38–1.27 (m, 4 H),
0.88 (t, J = 7.2 Hz, 3 H).
observed NOESY correlations
H
Hvinyl / CH2(allylic)
CH3(CH2)2CH2
H
SO2
CH2
CH3
CH2(allylic) / CH(aromatic)
Hvinyl / CH2(allylic)
4h
13C NMR (CDCl3): d = 144.7, 141.5, 139.2, 136.9, 133.2, 133.1,
129.1, 128.6, 127.6, 127.5, 126.2, 125.8, 36.3, 31.3, 28.5, 22.4,
13.9.
Figure 2
MS: m/z (%) = 340 (1.2) [M+], 169 (22), 156 (100), 141 (81), 128
(53), 115 (62), 91 (44).
(Z)-1-Phenyl-2-phenylsulfonyl-4-methyl-1,4-pentadiene (4i)
Colorless liquid.
Anal. Calcd for C21H24SO2: C, 74.08; H, 7.11. Found: C, 73.82; H,
7.17.
IR (film): 3064, 2922, 1651, 1491, 1446, 1305, 1147, 896, 748, 689
cm–1.
1H NMR (CDCl3): d = 7.53–7.41 (m, 3 H), 7.30–7.18 (m, 7 H), 7.05
(s, 1 H), 5.00 (s, 1 H), 4.95 (s, 1 H), 3.27 (s, 2 H), 1.76 (s, 3 H).
(1Z,4E)-1,5-Diphenyl-2-phenylsulfonyl-1,4-pentadiene (4f)
Colorless liquid.
13C NMR (CDCl3): d = 141.7, 141.5, 140.5, 139.9, 134.1, 132.8,
129.0, 128.4, 128.2, 127.8, 127.7, 114.9, 41.1, 21.8.
IR (film): 3058, 2957, 1714, 1598, 1446, 1305, 1147, 968, 747, 690
cm–1.
MS: m/z (%) = 298 (4.7) [M+], 157 (100), 141 (84), 128 (50), 115
(63), 91 (35), 77 (18).
1H NMR (CDCl3): d = 7.56–7.20 (m, 15 H), 7.10 (s, 1 H), 6.53 (d,
J = 16.0 Hz, 1 H), 6.26 (dt, J = 16.0, 6.8 Hz, 1 H), 3.48 (d, J = 6.8
Hz, 2 H).
13C NMR (CDCl3): d = 142.8, 140.5, 139.5, 136.8, 134.0, 133.8,
132.9, 129.0, 128.6, 128.5, 128.2, 127.8, 127.7, 126.3, 125.3, 36.5.
Anal. Calcd for C18H18SO2: C, 72.45; H, 6.08. Found: C, 72.19; H,
5.87.
MS: m/z (%) = 360 (1.5) [M+], 219 (25), 217 (100), 202 (44).
Acknowledgment
Anal. Calcd for C23H20SO2: C, 76.63; H, 5.59. Found: C, 76.40; H,
5.62.
We thank the National Natural Science Foundation of China (Pro-
ject No. 20462002) and the Natural Science Foundation of Jiangxi
Province of China (Project No. 0420015) for financial support.
(1E,4Z)-1-Phenyl-4-(4-methylphenyl)sulfonyl-6-methoxy-1,4-
hexadiene (4g)
Colorless liquid.
References
IR (film): 2922, 1650, 1595, 1450, 1300, 1151, 962, 827, 692 cm–1.
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129.9, 128.5, 127.8, 127.6, 126.2, 124.6, 69.6, 58.6, 35.4, 21.6.
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Synthesis 2007, No. 8, 1197–1203 © Thieme Stuttgart · New York

PAPER
One-Pot, Stereoselective Synthesis of 1,3- and 1,4-Dienyl Sulfones
1203
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