Regio- and stereo-selective synthesis of tetrasubstituted olefins by the three-component tandem reaction of phenylselenomagnesium bromide, acetylenic sulfones and allylic bromides

Article abstract of DOI:10.3184/030823410X12670432614319

Tetrasubstituted olefins containing a 1,4-diene structural unit can be regio- and stereo-selectively synthesised in good yields under mild conditions, in one pot, by Michael addition of phenylselenomagnesium bromide to acetylenic sulfones, followed by coupling with allylic bromides.

Full text of DOI:10.3184/030823410X12670432614319

JOURNAL OF CHEMICAL RESEARCH 2010
RESEARCH PAPER 127
MARCH, 127–129
Regio- and stereo-selective synthesis of tetrasubstituted olefins by the
three-component tandem reaction of phenylselenomagnesium bromide,
acetylenic sulfones and allylic bromides
Bin Huanga, Shengyong Youb and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
bInstitute of Applied Chemistry, Jiangxi Academy of Science, Nanchang 330029, P. R. China
Tetrasubstituted olefins containing a 1,4-diene structural unit can be regio- and stereo-selectively synthesised in
good yields under mild conditions, in one pot, by Michael addition of phenylselenomagnesium bromide to acetylenic
sulfones, followed by coupling with allylic bromides.
Keywords: acetylenic sulfone, Michael addition, vinyl sulfone, vinyl selenide, tetrasubstituted olefin
The stereo-selective synthesis of multifunctional alkenes
remains a challenging problem in organic synthesis and is still
being actively explored because many useful functional group
transformations can be achieved by introduction and removal
of metal or heteroatom functions.1–3 Difunctional group
reagents, which have two different functional groups linked to
the olefinic carbon atoms (such as Sn–Si,4 Sn–Mg,5 Sn–Zr,6
Sn–Se,7 Se–Zr,8 Se–Al,9 and Se–Cu10), are useful intermediates
in developing convenient methods for the stereocontrolled
synthesis of various substituted alkenes. Organomagnesium
reagents11,12 and vinyl selenides13 have been widely used as
building blocks in organic synthesis. However, the synthesis of
functionalised alkenes from Se–Mg difunctional reagents has
received less attention. Acetylenic sulfones are known as elec-
trophiles,14 whereas selenolate and its analogues are good
nucleophiles for Michael addition.15 The tandem reaction has
recently been of interest for organic synthesis because it offers
a convenient and economical method to prepare desired organic
molecules.16–19 Huang and Xie reported the stereo-selective
Michael–aldol tandem reaction of phenylselenomagnesium
bromide with acetylenic sulfones and carbonyl compounds,
providing a simple and efficient one-pot protocol for the syn-
thesis of difunctionalised tetrasubstituted alkenes.20 Recently,
we investigated the Michael addition of magnesium selenolate
to acetylenic sulfones to prepare Se–Mg difunctional reagents
which were captured by allylic bromides. Herein, we wish
to report that tetrasubstituted olefins containing a 1,4-diene
structural unit can be regio- and stereo-selectively synthesised
in good yields under mild conditions, in one pot, by Michael
addition of phenylselenomagnesium bromide to acetylenic
sulfones, followed by coupling with allylic bromides.
Acetylenic sulfones 1 were prepared according to a litera-
ture procedure.21 It is well known that the conjugate addition
of phenylselenomagnesium bromide to acetylenic sulfones 1
in THF/CH Cl2 (1:4 v/v) at –20 °C proceeds highly regio-
and stereo2-selectively to generate (Z)-α-arylsulfonyl-β-
phenylselenovinylmagnesium bromides 2. The Michael
addition of phenylselenomagnesium bromide to acetylenic
sulfones has been shown to take place in an anti-fashion.20
To extend the application of the conjugate addition of phenyl-
selenomagnesium bromide to acetylenic sulfones, considering
the fact that allylic bromides are efficient electrophiles and can
undergo cross-coupling reactions with organometallic reagents
under mild conditions, we investigated the cross-coupling
reaction of allylic bromides with (Z)-α-arylsulfonyl-β-
phenylselenovinylmagnesium bromides 2 obtained by the
conjugate addition of phenylselenomagnesium bromide to
acetylenic sulfones 1 in THF/CH2Cl2 (1:4 v/v) (Scheme 1).
At –20 °C, 1-phenylsulfonylhex-1-yne (1a) was added to
the solution of phenylselenomagnesium bromide in THF/
CH2Cl2 (1:4 v/v), which was prepared in situ from phenylmag-
nesium bromide and selenium powder. When the Michael
addition was complete (monitored by TLC), an allyl bromide
was added to the reaction mixture and the reaction mixture was
stirred at –20 °C for 2 h. The desired (4Z)-4-phenylsulfonyl-
5-phenylseleno-1,4-nonadiene (3a) was obtained in 84% yield
stereo-selectively. A series of acetylenic sulfones 1 were
subjected to the above reaction conditions and the results are
summarised in Table 1. From Table 1, we can see that the
Michael addition reactions of phenylselenomagnesium bro-
mide to a variety of acetylenic sulfones proceeded smoothly in
THF/CH2Cl2 (1:4 v/v) at –20 °C to afford the corresponding
Scheme 1
* Correspondent. E-mail:caimzhong@163.com

128 JOURNAL OF CHEMICAL RESEARCH 2010
1
Table 1 Synthesis of tetrasubstituted olefins containing a
687; H NMR (400 MHz, CDCl3): δ 7.99–8.01 (m, 2H), 7.53–7.34
1,4-diene structural unita
(m, 3H), 7.13–7.08 (m, 5H), 5.88 (m, 1H), 5.23 (m, 1H), 5.14 (d,
J = 9.6 Hz, 1H), 3.52 (d, J = 7.2 Hz, 2H), 2.84 (t, J = 8.0 Hz, 2H),
1.49–1.25 (m, 4H), 0.86 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.2, 140.0, 137.4, 133.3, 132.8, 132.2, 129.3, 129.1,
128.5, 128.4, 126.8, 119.2, 39.6, 32.5, 30.0, 22.4, 13.8; MS (EI):
m/z 419 (M+, 1.4), 157 (44), 115 (75), 77 (100); Anal. Calcd for
C21H24O2SSe: C, 60.13; H, 5.77. Found: C, 59.85; H, 5.53%.
Entry
R
Ar
R1
Product Yieldb/%
1
2
3
4
5
6
7
8
n-C H
n-C4H9
n-C44H99
Ph
Ph
H
3a
3b
3c
3d
3e
3f
84
81
79
83
78
75
80
82
Ph
CH3
H
4-CH C H
4-CH33C66H44
Ph
4-CH C H
4-CH33C66H44
Ph
H
(4Z)-2-Methyl-4-phenylsulfonyl-5-phenylselenonona-1,4-diene
Ph
CH
CH33
H
(3b): Oil. IR (film): ν (cm−1) 3067, 2929, 1644, 1577, 1477, 1307,
Ph
1
n-C H13
3g
3h
1149, 1084, 723, 687; H NMR (400 MHz, CDCl3): δ 8.01–7.99
n-C66H13
H
(m, 2H), 7.53–7.36 (m, 3H), 7.13–7.08 (m, 5H), 4.96 (s, 1H), 4.92
(d, J = 1.2 Hz, 1H), 3.52 (s, 2H), 2.85 (t, J = 8.0 Hz, 2H), 1.85 (s, 3H),
1.47–1.23 (m, 4H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.7, 140.5, 133.9, 133.2, 132.3, 129.3, 129.1, 128.5,
128.3, 127.2, 126.7, 115.4, 39.6, 34.8, 32.6, 22.4, 22.0, 13.8; MS (EI):
m/z 433 (M+, 1.1), 157 (26), 115 (63), 77 (100); Anal. Calcd for
C22H26O2SSe: C, 60.95; H, 6.05. Found: C, 60.70; H, 6.21%.
a The reaction was performed with 0.5 mmol of acetylenic sul-
fone 1, 0.6 mmol of phenylselenomagnesium bromide, and
0.5 mmol of allylic bromide in THF/CH2Cl2 (1/4 v/v) at –20 °C
for 2 h.
b Isolated yield based on 1 used.
(4Z)-4-(p-Tolylsulfonyl)-5-phenylseleno-1,4-nonadiene (3c): Oil.
IR (film): ν (cm−1) 3058, 2927, 1633, 1596, 1477, 1302, 1148, 1084,
736, 676; H NMR (400 MHz, CDCl3): δ 7.88 (d, J = 7.6 Hz, 2H),
intermediates 2, which were captured by allylic bromides to
give stereo-selectively tetrasubstituted olefins containing a
1,4-diene structural unit in good yields. However, when allylic
chlorides were used as the electrophiles, the cross-coupling
reactions of intermediates 2 did not occur and none of the
desired products were obtained.
The (4Z)-configuration of compound 3c was confirmed by
NOESY NMR experiments. There was a correlation between
the allylic protons (δ = 2.84 ppm) of the butyl group and
the allylic protons (δ = 3.51 ppm) of the allyl group. No
correlation between the allylic protons (δ = 2.84 ppm) of the
butyl group and the aromatic protons (δ = 7.88 ppm) of the
p-tolylsulfonyl group was observed. The NOE results indicate
that 3c has the expected (4Z)-configuration and the cross-
coupling reaction of the intermediates 2 with allylic bromides
occurs with retention of configuration of the starting
intermediates 2.
In summary, an efficient and stereo-selective one-pot
synthetic method for tetrasubstituted olefins containing a 1,4-
diene structural unit has been developed by Michael addition
of phenylselenomagnesium bromide to acetylenic sulfones,
followed by coupling with allylic bromides. The present
method has the advantages of readily conditions and good
yields. These tetrasubstituted olefins may be potential precur-
sors in the synthesis of natural products and in other synthetic
transformations.
1
7.18–7.07 (m, 7H), 5.87 (m, 1H), 5.23 (m, 1H), 5.13 (d, J = 10.0 Hz,
1H), 3.51 (d, J = 7.2 Hz, 2H), 2.84 (t, J = 8.0 Hz, 2H), 2.36 (s, 3H),
1.48-1.24 (m, 4H), 0.87 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 166.5, 144.2, 137.5, 137.0, 132.9, 132.3, 129.3, 129.1,
129.0, 128.5, 126.6, 119.2, 39.6, 32.5, 30.0, 22.4, 21.6, 13.8; MS (EI):
m/z 433 (M+, 1.5), 157 (46), 139 (54), 115 (68), 91 (100), 77 (51);
Anal. Calcd for C22H26O2SSe: C, 60.95; H, 6.05. Found: C, 60.68;
H, 6.13%.
(1Z)-1-Phenyl-1-phenylseleno-2-(p-tolylsulfonyl)penta-1,4-diene
(3d): Oil. IR (film): ν (cm−1) 3057, 1636, 1597, 1313, 1146, 1084, 810,
1
690; H NMR (400 MHz, CDCl3): δ 8.12 (d, J = 8.0 Hz, 2H), 7.39
(d, J = 8.0 Hz, 2H), 7.13–7.06 (m, 3H), 6.96–6.91 (m, 5H), 6.69–6.67
(m, 2H), 5.54 (m, 1H), 5.01 (m, 1H), 4.93 (d, J = 10.0 Hz, 1H), 3.33
(d, J = 8.0 Hz, 2H), 2.49 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 164.5, 144.5, 139.4, 137.4, 137.2, 133.5, 129.8, 129.4, 128.5, 128.4,
128.3, 128.2, 127.4, 127.1, 122.8, 117.9, 34.5, 21.8; MS (EI): m/z 453
(M+, 1.2), 361 (15), 269 (22), 220 (100), 91 (46); Anal. Calcd for
C24H22O2SSe: C, 63.56; H, 4.89. Found: C, 63.29; H, 5.07%.
(1Z)-1-Phenyl-1-phenylseleno-2-phenylsulfonyl-4-methylpenta-1,4-
diene (3e): Oil. IR (film): ν (cm−1) 3056, 1644, 1577, 1315, 1146,
1
1085, 816, 687; H NMR (400 MHz, CDCl ): δ 8.12–8.10 (m, 2H),
7.51–7.46 (m, 2H), 7.25–6.84 (m, 11H), 4.713(d, J = 1.2 Hz, 1H), 4.60
(s, 1H), 2.73 (s, 2H), 1.65 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 165.3, 140.1, 139.5, 133.5, 132.4, 131.0, 129.6, 128.8, 128.7, 128.6,
128.1, 128.0, 127.4, 127.2, 127.0, 115.1, 37.2, 21.7; MS (EI): m/z 453
(M+, 2.1), 178 (53), 155 (62), 105 (100), 97 (69), 77 (52); Anal. Calcd
for C24H22O2SSe: C, 63.56; H, 4.89. Found: C, 63.35; H, 4.61%.
(1Z)-1-Phenyl-1-phenylseleno-2-(p-tolylsulfonyl)-4-methylpenta-1,4-
diene (3f): Oil. IR (film): ν (cm−1) 3058, 1642, 1597, 1318, 1140,
Experimental
1
1085, 811, 669; H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.4 Hz,
1
IR spectra were obtained using a Perkin-Elmer 683 instrument. H
2H), 7.28–6.83 (m, 12H), 4.71 (t, J = 1.2 Hz, 1H), 4.60 (s, 1H), 2.72
(s, 2H), 2.42 (s, 3H), 1.65 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 164.6, 144.5, 140.2, 139.6, 137.1, 132.6, 130.9, 129.3, 128.8, 128.5,
128.1, 128.0, 127.9, 127.3, 126.9, 115.0, 37.1, 21.8, 21.7; MS (EI):
m/z 467 (M+, 1.2), 314 (36), 178 (97), 155 (99), 91 (100), 77 (96);
Anal. Calcd for C25H24O2SSe: C, 64.23; H, 5.17. Found: C, 64.38;
H, 5.41%.
NMR spectra were recorded on a Bruker AC-P400 (400 MHz) spec-
trometer with TMS as an internal standard using CDCl3 as the solvent.
13C NMR spectra were recorded on a Bruker AC-P400 (100 MHz)
spectrometer using CDCl3 as the solvent. Mass spectra (EI) were
determined with a Finnigan 8230 mass spectrometer. Microanalyses
were obtained using a Perkin-Elmer 240 elemental analyzer. THF
was distilled from sodium-benzophenone immediately prior to use
and CH2Cl2 was distilled from P O immediately prior to use. Other
reagents were used as received w2ith5out further purification.
(4Z)-4-(p-Tolylsulfonyl)-5-phenylselenoundeca-1,4-diene (3g): Oil.
IR (film): ν (cm−1) 3057, 2926, 1635, 1597, 1478, 1305, 1146, 1081,
1
737, 679; H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 8.0 Hz, 2H),
7.19–7.08 (m, 7H), 5.86 (m, 1H), 5.22 (m, 1H), 5.13 (d, J = 10.0 Hz,
1H), 3.52 (d, J = 7.2 Hz, 2H), 2.85 (t, J = 8.0 Hz, 2H), 2.35 (s, 3H),
1.49–1.23 (m, 8H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 166.1, 144.3, 137.3, 137.1, 132.8, 132.2, 129.4, 129.2,
129.1, 128.4, 126.5, 119.3, 39.7, 35.7, 31.6, 29.3, 29.0, 22.6, 21.6,
14.0; MS (EI): m/z 461 (M+, 1.3), 157 (37), 115 (63), 91 (100),
77 (82); Anal. Calcd for C24H30O2SSe: C, 62.45; H, 6.55. Found:
C, 62.19; H, 6.33%.
General procedure for the synthesis of tetrasubstituted olefins
containing a 1,4-diene structural unit
To
a colourless solution of phenylselenomagnesium bromide
(0.6 mmol) in THF/CH2Cl2 (v/v = 1:4, 5 mL) was added acetylenic
sulfone (0.5 mmol) at –20 °C. The reaction mixture was stirred at
–20 °C for 10 min, then allylic bromide (0.5 mmol) was added and the
resulting mixture was stirred at –20 °C for 2 h and room temperature
for 1h, quenched with a saturated NH Cl solution (10 mL) and
extracted with diethyl ether (3 × 20 mL4). The organic layer was
combined, washed with water (3 × 10 mL), and dried over MgSO4.
After filtration and removal of solvent under reduced pressure, the
residue was purified by column chromatography on silica gel (eluent:
light petroleum ether/Et2O, 5:1).
(4Z)-4-Phenylsulfonyl-5-phenylselenoundeca-1,4-diene (3h): Oil.
IR (film): ν (cm−1) 3057, 2928, 1631, 1579, 1475, 1307, 1149, 1085,
1
725, 689; H NMR (400 MHz, CDCl ): δ 8.00–8.02 (m, 2H), 7.54–
7.35 (m, 3H), 7.14–7.09 (m, 5H), 5.839 (m, 1H), 5.22 (m, 1H), 5.14
(d, J = 9.6 Hz, 1H), 3.53 (d, J = 7.2 Hz, 2H), 2.85 (t, J = 8.0 Hz, 2H),
1.50–1.24 (m, 8H), 0.87 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.3, 140.1, 137.3, 133.4, 132.9, 132.3, 129.4, 129.2,
128.6, 128.5, 126.9, 119.1, 39.5, 35.6, 31.78, 29.3, 29.1, 22.7, 14.1;
(4Z)-4-Phenylsulfonyl-5-phenylselenonona-1,4-diene (3a): Oil. IR
(film): ν (cm−1) 3059, 2926, 1634, 1577, 1477, 1305, 1148, 1084, 723,

JOURNAL OF CHEMICAL RESEARCH 2010 129
MS (EI): m/z 447 (M+, 1.5), 157 (49), 115 (70), 77 (100); Anal. Calcd
for C23H28O2SSe: C, 61.73; H, 6.31. Found: C, 61.97; H, 6.48%.
5
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We thank the National Natural Science Foundation of China
(Project No. 20862008) and the Natural Science Foundation of
Jiangxi Province in China (Project No.2007GZW0172) for
financial support.
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Received 24 October 2009; accepted 27 January 2010
Paper 090839 doi: 10.3184/030823410X12670432614319
Published online: 22 March 2010
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