Stereoselective synthesis of difunctionalized 1,3-dienes containing tin and sulfonyl groups by palladium-catalyzed regio-and stereocontrolled addition reactions

Article abstract of DOI:10.1002/ejoc.201101153

Using palladium-catalyzed addition reactions, a terminal alkyne, an acetylenic sulfone, and a tin hydride comprise the building blocks for the construction of difunctionalized 1,3-dienes containing tin and sulfonyl groups in an atom-economical fashion. Te

Full text of DOI:10.1002/ejoc.201101153

FULL PAPER
DOI: 10.1002/ejoc.201101153
Stereoselective Synthesis of Difunctionalized 1,3-Dienes Containing Tin and
Sulfonyl Groups by Palladium-Catalyzed Regio- and Stereocontrolled Addition
Reactions
Hong Zhao,*[a] Weisen Yang,[b] Shiyun Xie,[c] and Mingzhong Cai*[c]
Keywords: Alkenes / Palladium / Tin / Sulfur / Enynes
Using palladium-catalyzed addition reactions, a terminal alk-
yne, an acetylenic sulfone, and a tin hydride comprise the
building blocks for the construction of difunctionalized 1,3-
amounts of palladium acetate and tri(2,6-dimethoxyphenyl)-
phosphane to give (E)-1-sulfonyl-substituted 1,3-enynes 3 in
excellent yields. Hydrostannylation of 1,3-enynes 3 with tri-
dienes containing tin and sulfonyl groups in an atom-eco- butyltin hydride in the presence of Pd(PPh3)4 affords regio-
nomical fashion. Terminal alkynes 1 undergo clean cis ad- and stereoselectively (1E,3E)-1-sulfonyl-3-tributylstannyl-
dition to acetylenic sulfones 2 in the presence of catalytic
substituted 1,3-dienes 4 in excellent yields.
(aryl)thiobuta-1,3-dienes by Negishi coupling of α-alkyl-
(aryl)thiovinylzinc chloride and α-bromovinyl ether.[16]
Coleman et al. reported the stereoselective synthesis of
(E,E)-1-tributylstannyl-4-borylbuta-1,3-diene and its use as
an orthogonal Stille and Suzuki–Miyaura coupling part-
ner.[17] Recently, we described the stereoselective synthesis
of (Z,Z)-2-silyl-3-stannyl-substituted 1,3-dienes through the
hydromagnesiation of alkynylsilanes, followed by cross-
coupling with (E)-α-iodovinylstannanes catalyzed by
Pd(PPh3)4[18] and the stereoselective synthesis of difunction-
alized 1,3-dienes containing tin and halogen by hydrozir-
conation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes.[19] How-
ever, to the best of our knowledge, no well-established
method has been used to prepare stereoselectively (1E,3E)-
1-sulfonyl-3-(tributylstannyl)-substituted 1,3-dienes. Herein,
we wish to report that (1E,3E)-1-sulfonyl-3-(tributylstann-
yl)-substituted 1,3-dienes could be conveniently synthe-
sized by the cis addition of terminal alkynes to acetylenic
sulfones in the presence of a catalytic amount of palladium
acetate and tri(2,6-dimethoxyphenyl)phosphane (2,6-
TDMPP), followed by palladium-catalyzed hydrostann-
ylation with tributyltin hydride (Scheme 1).
Introduction
The stereocontrolled synthesis of 1,3-dienes containing
metal or heteroatom functional groups has attracted much
attention in organic synthesis because many useful func-
tional group transformations can be achieved by introduc-
tion and removal of metal or heteroatom functions. In ad-
dition, heteroatom-substituted 1,3-dienes can control both
regio- and stereoselectivity and play a very important role
in cycloadditions.[1] The stereoselective synthesis of 1,3-di-
enyl sulfides,[2] 1,3-dienyl selenides,[3] 1,3-dienylsilanes,[4]
1,3-dienylstannanes,[5] and 1,3-dienyl sulfones[6] has already
been described. Recently, the synthesis of difunctionalized
1,3-dienes containing metal or heteroatom functional
groups has also attracted great interest in organic synthesis,
as such dienes may find use as synthetic building blocks.[7]
The synthesis of 2,3-bisboryl-1,3-dienes,[8] 1,4-dihalo-1,3-
dienes,[9] 1-sulfonyl-4-phenylseleno-1,3-dienes,[10] 2-sulfonyl-
3-phenylseleno-1,3-dienes,[11]
1-bromo-4-phenylthio-1,3-
dienes,[12] 5-tosyl-2,4-pentadienamides,[13] 2-phenylsulfonyl-
3-phenylselenobuta-1,3-diene,[14] and 2,3- or 1,3-bis(phenyl-
sulfonyl)buta-1,3-dienes[15] has been described. Jin et al. re-
ported the stereoselective synthesis of 2-alkoxy-3-alkyl-
[a] School of Chemistry and Chemical Engineering,
Guangdong Pharmaceutical University,
Guangzhou 510006, P. R. China
E-mail: zhaohong1001@sina.com
[b] Department of Chemistry and Environment Engineering,
Key Laboratory for Green Chemical Technology of
Fujian Higher Education, Wuyi University,
Wuyishan 354300, P. R. China
[c] Department of Chemistry, Jiangxi Normal University,
Nanchang 330022, P. R. China
Fax: +86-791-88120388
E-mail: caimzhong@163.com
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201101153.
Scheme 1. Synthesis of difunctionalized 1,3-dienes containing tin
and sulfonyl groups.
Eur. J. Org. Chem. 2012, 831–836
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
831

H. Zhao, W. Yang, S. Xie, M. Cai
FULL PAPER
Palladium-catalyzed hydrostannylation of alkynes pro-
vides a simple general route for the synthesis of vinylstann-
anes.[21] The palladium-catalyzed hydrostannylation of sub-
stituted enynes generally leads to the α-addition product
(addition of the tin atom at the acetylenic carbon atom ad-
jacent to the vinylic carbon atom), providing a convenient
route for the synthesis of 1,3-dienylstannanes. The hydro-
stannylation of chloroenynes and alkyl-substituted en-
ynes,[22] enediynes,[23] and eneynols[5c] has been reported.
Recently, we reported that the Pd-catalyzed hydrostan-
nylation of acetylenic sulfones gave highly regio- and stereo-
selectively (E)-α-stannylvinyl sulfones in excellent yields.[24]
The excellent α-regioselectivity observed is due to polariza-
tion of the acetylenic bond resulting in addition of hydride
to the more electron-deficient β-carbon of the triple bond
(placing the tin moiety α). To prepare (1E,3E)-1-sulfonyl-3-
(tributylstannyl)-substituted 1,3-dienes regio- and stereose-
lectively, we investigated the palladium-catalyzed hydro-
Results and Discussion
One general approach for the synthesis of 1-sulfonyl-sub-
stituted 1,3-enynes involved the addition of methyl phenyl
sulfone to α,β-acetylenic aldehydes or ketones in the pres-
ence of a base and the subsequent dehydration of the ad-
dition products by using methanesulfonyl chloride and tri-
ethylamine as dehydrating agents, but low yields and poor
stereoselectivity were usually obtained.[10] Trost et al.[20] re-
ported that the cis addition reaction of terminal alkynes to
alkynoates proceeded highly regioselectively in the presence
of catalytic amounts of Pd(OAc)2 and tri(2,6-dimeth-
oxyphenyl)phosphane to give (E)-2-en-4-ynoates. We found
that the cis addition reaction of terminal alkynes 1 to acet-
ylenic sulfones 2 could also proceed smoothly in the pres-
ence of Pd(OAc)2 (2 mol-%) and tri(2,6-dimethoxyphenyl)-
phosphane (2 mol-%) in 1,2-dichloroethane at room tem-
perature to produce highly regio- and stereoselectively (E)-
1-sulfonyl-substituted 1,3-enynes 3 in excellent yields after
6 h (Scheme 1). Typical results are summarized in Table 1.
A variety of terminal alkynes and acetylenic sulfones could
be used as the substrates, and the isolation of the products
only involved direct flash chromatography to give the de-
sired (E)-1-sulfonyl-substituted 1,3-enynes 3. Analysis of
crude products 3 by 1H NMR spectroscopy (400 MHz)
showed the isomeric purities to be higher than 99%. One
olefinic proton signal of compounds 3a–d, 3h, and 3i ap-
pears as a singlet at δ = 6.45–6.67 ppm, which indicates that
the addition reaction of terminal alkynes 1 to acetylenic
sulfones 2 had taken place with strong preference for the
addition of the hydrogen atom at the carbon atom adjacent
to the benzenesulfonyl group. The (1E)-configuration of
compound 3a was confirmed by NOESY. A correlation be-
tween the allylic protons (δ = 2.65 ppm) and the aromatic
protons was observed. There was no correlation between
the vinylic proton (δ = 6.45 ppm) and the allylic protons (δ
= 2.65 ppm). The NOE results indicated that compound 3a
had the expected (E) configuration and that a terminal alk-
yne could undergo clean cis-1,2-addition to an internal
acetylenic sulfone in the presence of catalytic amounts of
Pd(OAc)2 and 2,6-TDMPP in 1,2-dichloroethane.
stannylation of (E)-1-sulfonyl-substituted 1,3-enynes
3
(Scheme 1).
Our initial efforts were devoted to the selection of an
efficient catalyst and a suitable solvent for efficient hydro-
stannylation of (E)-1-sulfonyl-substituted 1,3-enynes 3 with
Bu3SnH. Thus, (E)-2-butyl-1-(benzenesulfonyl)oct-1-en-3-
yne (3a, 1 mmol) and Bu3SnH (1.1 mmol) were treated in
THF or benzene (2 mL), at room temperature with Pd0 and
PdII catalysts (Table 2). Among the palladium catalysts
tested [Pd(OAc)2, Pd(PPh3)4, PdCl2(PPh3)2, and PdCl2],
Pd(PPh3)4 proved to be the most efficient. Both THF and
benzene could be used as solvent, but THF was the best
choice. Increasing the amount of Pd(PPh3)4 could shorten
the reaction time, but did not increase the yield of 4a. Taken
together, an excellent result was obtained when the hydro-
stannylation reaction was carried out with Pd(PPh3)4
(2 mol-%) in THF at room temperature for 4 h under an
argon atmosphere (Table 2, Entry 5).
Table 2. Influence of catalyst and solvent in the hydrostannylation
reaction.[a]
Entry
Catalyst (mol-%)
Solvent Time [h] Yield 4a [%][b]
1
2
3
4
5
6
7
8
9
Pd(OAc)2 (2)
Pd(OAc)2 (2)
PdCl2(PPh3)2 (2)
PdCl2(PPh3)2 (2)
Pd(PPh3)4 (2)
Pd(PPh3)4 (2)
Pd(PPh3)4 (5)
PdCl2 (2)
THF
benzene
THF
benzene
THF
benzene
THF
THF
24
24
8
8
4
8
2
24
24
0
0
65
52
91
73
90
0
Table 1. Synthesis of (E)-1-sulfonyl-substituted 1,3-enynes 3.[a]
Entry
R1
R
Product
Yield [%][b]
PdCl2 (2)
benzene
0
1
2
3
4
5
6
7
8
9
n-C4H9
Ph
CH2OH
n-C4H9
n-C4H9
n-C4H9
3a
3b
3c
3d
3e
3f
3g
3h
3i
89
91
87
88
92
90
88
86
87
[a] Reaction was performed with 3a (1 mmol), Bu3SnH (1.1 mmol),
solvent (2 mL) at room temperature under Ar. [b] Isolated yield.
CH3OCH2CH2 n-C4H9
n-C4H9
Ph
CH2OH
n-C4H9
Ph
Ph
Ph
Ph
To examine the scope of this reaction, the hydrostann-
ylation reactions of a variety of (E)-1-sulfonyl-substituted
1,3-enynes 3 with Bu3SnH were investigated under the opti-
mum experimental conditions, and the results are listed in
Table 3. The reactions proceeded smoothly in the presence
CH3OCH2CH2
CH3OCH2CH2
[a] Reaction conditions: terminal alkyne (10 mmol), acetylenic sulf-
one (10 mmol), Pd(OAc)2 (0.2 mmol), 2,6-TDMPP (0.2 mmol), 1,2-
dichloroethane (10 mL), room temperature, 6 h. [b] Isolated yield.
832
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Eur. J. Org. Chem. 2012, 831–836

Stereoselective Synthesis of 1,3-Dienes Containing Tin and Sulfonyl Groups
Scheme 2. Mechanistic rationale for the hydrostannylation of (E)-1-sulfonyl-substituted 1,3-enynes.
of Pd(PPh3)4 (2 mol-%) in THF at room temperature to af- stereochemistry of the addition was readily apparent from
ford highly regio- and stereoselectively the corresponding the 1H NMR spectra of compounds 4, which showed
(1E,3E)-1-sulfonyl-3-(tributylstannyl)-substituted 1,3-dienes 3J
= 56–64 Hz, fully in accord with an E geometry
119Sn,H
4 in excellent yields. In all cases, a single regio- and geomet- and overall cis addition of tin hydride.[25] The (3E)-configu-
ric isomer was formed according to Scheme 1, and the iso- ration of compounds 4 could also be confirmed by the fact
3
13C,119Sn
lation of the products only involved direct flash chromatog- that values of J
lie between 21 and 56 Hz in their
raphy.
13C NMR spectra, indicating that the R1 substituent at C(4)
is trans with respect to the Bu3Sn group attached to C(3).[26]
A possible mechanism for the hydrostannylation of (E)-1-
sulfonyl-substituted 1,3-enynes 3 is outlined in Scheme 2.
The mechanism is based upon those proposed by
Greeves,[27] Gevorgyan,[28] and Lautens.[29] Oxidative ad-
dition of Bu3SnH to Pd0 provides PdII complex A. Coordi-
nation of the triple bond with A leads to complex B, which
may then undergo insertion of the triple bond to the Pd–
H bond to give vinylpalladium(II) complex C followed by
reductive elimination to furnish vinylstannane 4.
Table 3. Synthesis of (1E,3E)-1-sulfonyl-3-(tributylstannyl)-substi-
tuted 1,3-dienes 4.[a]
Entry
R
R1
Product
Yield [%][b]
1
2
3
4
5
6
n-C4H9
n-C4H9
n-C4H9
Ph
n-C4H9
Ph
CH2OH
n-C4H9
4a
4b
4c
4d
4e
4f
91
92
89
93
86
88
CH3OCH2CH2 n-C4H9
CH3OCH2CH2 Ph
[a] Reaction was performed with 3 (1 mmol), Bu3SnH (1.1 mmol),
Pd(PPh3)4 (0.02 mmol), THF (2 mL) at room temperature under
an argon atmosphere for 4 h. [b] Isolated yield.
We have also carried out the Stille cross-coupling reac-
tion of compound 4a with aryl iodides in the presence of
Pd(PPh3)4 (5 mol-%) and CuI (75 mol-%) in DMF at room
temperature to afford 1,3-dienyl sulfones 5a and 5b in good
yields (Scheme 3).
The regioselectivity could be easily assessed by the ap-
propriate coupling patterns of the vinylic proton. One ole-
finic proton signal of compounds 4a, 4c, 4d, and 4e splits
characteristically into one triplet at δ = 5.52–5.75 ppm with
J = 6.4–7.6 Hz, which indicates that the hydrostannylation
to compounds 3 has taken place with a strong preference
for the addition of the hydride at the more electron-de-
ficient terminus of the acetylene. In all cases, a single re-
gioisomer (3-stannylated dienyl sulfone) 4 was formed in
high yield according to Scheme 1 and no 4-stannylated di-
enyl sulfone was isolated due to the presence of strongly
electron-withdrawing sulfonyl groups. A reasonable expla-
nation lies in the strong electronic polarization of the
acetylene through conjugation to the sulfone moiety, which
occurs in a manner analogous to that observed with acetyle-
Scheme 3. Stille coupling of 4a with aryl iodides.
Conclusions
In summary, we have developed a highly efficient ap-
nic sulfones, as the palladium-catalyzed hydrostannylation proach for the stereoselective synthesis of difunctionalized
of acetylenic sulfones is highly regio- and stereoselective.[24] 1,3-dienes containing tin and sulfonyl groups by the cis ad-
In addition, no bis-stannylated derivatives produced by the dition of terminal alkynes to acetylenic sulfones in the pres-
addition of Bu3SnSnBu3 to the triple bonds were detected, ence of catalytic amounts of Pd(OAc)2 and tri(2,6-dimeth-
which demonstrates the efficiency of the strategy. The oxyphenyl)phosphane, followed by palladium-catalyzed hy-
Eur. J. Org. Chem. 2012, 831–836
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
833

H. Zhao, W. Yang, S. Xie, M. Cai
FULL PAPER
m/z (%) = 279 (1.8) [M+ + 1], 153 (100), 141 (48), 117 (62), 91 (72),
drostannylation with tributyltin hydride. The present
method has some attractive advantages including the ready
availability of the starting materials, mild reaction condi-
tions, high regio- and stereoselectivity, and excellent yields.
Investigations into the synthetic applications of compounds
4 are currently in progress.
77 (95), 51 (61). IR (neat): ν = 3505, 3062, 2959, 2932, 2872, 2221,
˜
1578, 1447, 1307, 1147, 1085, 820, 754, 688 cm–1. C15H18O3S
(278.38): calcd. C 64.72, H 6.52; found C 64.45, H 6.28.
(E)-1-(Benzenesulfonyl)-2-butyl-6-methoxyhex-1-en-3-yne
(3d):
1
Yield: 2.69 g, 88%. Oil. H NMR (400 MHz, CDCl3): δ = 7.90 (d,
J = 8.0 Hz, 2 H), 7.62 (t, J = 8.0 Hz,1 H), 7.54 (t, J = 8.0 Hz, 2
H), 6.47 (s, 1 H), 3.50 (t, J = 6.6 Hz, 2 H), 3.36 (s, 3 H), 2.65 (t, J
= 7.8 Hz, 2 H), 2.61 (t, J = 6.6 Hz, 2 H), 1.50–1.47 (m, 2 H), 1.35–
1.30 (m, 2 H), 0.90 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 141.90, 141.41, 133.32, 133.22, 129.23 (2 C), 127.33 (2
C), 95.27, 80.38, 70.21, 58.74, 31.56, 30.28, 22.35, 20.80,
13.87 ppm. MS (EI): m/z (%) = 306 (1.1) [M]+, 205 (33), 123 (43),
Experimental Section
General: All chemicals were reagent grade and used as purchased.
Pd(OAc)2 was purchased from Aldrich with purity of 99.9%. The
products were purified by flash chromatography on silica gel. A
mixture of light petroleum ether (30–60 °C) and ethyl ether was
generally used as eluent. All products were characterized by com-
parison of their spectra and physical data with authentic samples.
91 (100), 77 (60). IR (neat): ν = 3003, 2961, 2931, 2875, 2222, 1578,
˜
1447, 1362, 1308, 1222, 1150, 1086, 734 cm–1. C17H22O3S (306.43):
calcd. C 66.63, H 7.24; found C 66.79, H 7.02.
1
IR spectra were recorded with a Perkin–Elmer 683 instrument. H
(E)-1-(Benzenesulfonyl)-2-phenyloct-1-en-3-yne (3e): Yield: 2.98 g,
92%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.62–7.59 (m, 2 H),
7.52–7.46 (m, 2 H), 7.38–7.26 (m, 6 H), 6.80 (s, 1 H), 2.34 (t, J =
7.0 Hz, 2 H), 1.52–1.45 (m, 2 H), 1.40–1.33 (m, 2 H), 0.88 (t, J =
7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 141.00,
138.31, 133.12, 130.20, 129.38, 128.86 (2 C), 128.78 (2 C), 128.50,
127.87 (2 C), 127.68 (2 C), 100.60, 80.30, 30.18, 21.97, 19.40,
13.53 ppm. MS (EI): m/z (%) = 324 (28) [M]+, 141 (100), 77 (82),
NMR spectra were recorded with a Bruker AC-P400 (400 MHz)
spectrometer with TMS as an internal standard in CDCl3. 13C
NMR spectra were recorded with a Bruker AC-P400 (100 MHz)
spectrometer in CDCl3. Mass spectra (EI, 70 eV) were recorded
with a Finnigan 8230 mass spectrometer. Microanalyses were mea-
sured by using a Yanaco MT-3 CHN microelemental analyzer.
General Procedure for the Palladium-Catalyzed Addition Reaction of
Terminal Alkynes to Acetylenic Sulfones: To a solution of acetylenic
sulfone (10.0 mmol) and terminal alkyne (10.0 mmol) in 1,2-dichlo-
roethane (8.0 mL) was added a solution of Pd(OAc)2 (0.2 mmol)
and 2,6-TDMPP (0.2 mmol) in 1,2-dichloroethane (2.0 mL) at
room temperature under an argon atmosphere. The reaction mix-
ture was stirred at room temperature for 6 h and concentrated un-
der reduced pressure. The residue was purified by column
chromatography (light petroleum ether/diethyl ether, 3:1) on silica
gel.
57 (45). IR (neat): ν = 3060, 2958, 2932, 2872, 2212, 1693, 1603,
˜
1560, 1447, 1307, 1149, 1084, 688 cm–1. C20H20O2S (324.45): calcd.
C 74.06, H 6.22; found C 74.23, H 5.98.
(E)-1-(Benzenesulfonyl)-2,4-diphenylbut-1-en-3-yne (3f): Yield:
1
3.10 g, 90%. White solid. H NMR (400 MHz, CDCl3): δ = 7.66–
7.29 (m, 15 H), 6.97 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 140.96, 137.41, 135.28, 134.17, 133.24, 131.99 (2 C), 129.67,
129.61, 129.05 (2 C), 128.86 (2 C), 128.49 (2 C), 128.01 (2 C),
127.75 (2 C), 121.56, 97.66, 88.34 ppm. MS (EI): m/z (%) = 344
(E)-1-(Benzenesulfonyl)-2-butyloct-1-en-3-yne (3a): Yield: 2.71 g,
89%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.92–7.90 (m, 2 H),
7.62–7.52 (m, 3 H), 6.45 (s, 1 H), 2.65 (t, J = 7.6 Hz, 2 H), 2.33 (t,
(17) [M]+, 267 (35), 141 (48), 77 (100). IR (KBr): ν = 3059, 2197,
˜
1582, 1597, 1555, 1489, 1446, 1307, 1148, 1084, 756, 688 cm–1.
C22H16O2S (344.44): calcd. C 76.72, H 4.68; found C 76.44, H 4.51.
J = 6.8 Hz, 2 H), 1.52–1.29 (m, 8 H), 0.92–0.85 (m, 6 H) ppm. 13
C
(E)-1-(Benzenesulfonyl)-5-hydroxy-2-phenylpent-1-en-3-yne
(3g):
NMR (100 MHz, CDCl3): δ = 142.03, 142.01, 133.27, 132.59,
129.22 (2 C), 127.30 (2 C), 99.11, 79.69, 31.70, 30.31, 30.26, 22.34,
21.91, 19.19, 13.89, 13.51 ppm. MS (EI): m/z (%) = 304 (21) [M]+,
Yield: 2.62 g, 88%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.61–
7.59 (m, 2 H), 7.52 (t, J = 7.6 Hz, 1 H), 7.39–7.28 (m, 7 H), 6.87
(s, 1 H), 4.39 (s, 2 H), 2.04 (s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 140.59, 136.69, 136.04, 133.72, 133.37, 129.69, 128.92
(2 C), 128.89 (2 C), 128.02 (2 C), 127.71 (2 C), 95.86, 84.37,
51.36 ppm. MS (EI): m/z (%) = 298 (25) [M]+, 141 (100), 77 (63).
275 (41), 141 (57), 77 (42), 57 (100). IR (neat): ν = 3064, 2958,
˜
2932, 2872, 2219, 1577, 1466, 1447, 1315, 1148, 1086, 818, 753,
688 cm–1. C18H24O2S (304.46): calcd. C 71.01, H 7.95; found C
70.73, H 7.72.
IR (neat): ν = 3491, 3061, 2211, 1602, 1584, 1563, 1447, 1307, 1149,
˜
(E)-1-(Benzenesulfonyl)-2-butyl-4-phenylbut-1-en-3-yne (3b): Yield:
1084, 803, 730, 688 cm–1. C17H14O3S (298.37): calcd. C 68.44, H
4.73; found C 68.26, H 4.47.
1
2.95 g, 91%. Oil. H NMR (400 MHz, CDCl3): δ = 7.96–7.94 (m,
2 H), 7.64–7.53 (m, 3 H), 7.44–7.31 (m, 5 H), 6.62 (s, 1 H), 2.78 (t,
J = 7.6 Hz, 2 H), 1.61–1.55 (m, 2 H), 1.42–1.35 (m, 2 H), 0.93 (t,
J = 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 141.85,
140.90, 133.44, 133.40, 131.96 (2 C), 129.52, 129.31 (2 C), 128.52
(2 C), 127.40 (2 C), 121.68, 96.58, 87.90, 31.41, 30.43, 22.38,
13.92 ppm. MS (EI): m/z (%) = 324 (16) [M]+, 295 (38), 141 (74),
(E)-1-(Benzenesulfonyl)-2-(2-methoxyethyl)oct-1-en-3-yne
(3h):
Yield: 2.63 g, 86%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.95–
7.92 (m, 2 H), 7.62–7.52 (m, 3 H), 6.50 (s, 1 H), 3.60 (t, J = 6.4 Hz,
2 H), 3.32 (s, 3 H), 3.01 (t, J = 6.4 Hz, 2 H), 2.34 (t, J = 6.8 Hz, 2
H), 1.52–1.48 (m, 2 H), 1.42–1.36 (m, 2 H), 0.90 (t, J = 7.2 Hz, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 141.56, 138.07, 133.92,
133.39, 129.23 (2 C), 127.48 (2 C), 99.70, 79.20, 70.23, 58.63, 31.81,
30.21, 21.94, 19.24, 13.54 ppm. MS (EI): m/z (%) = 306 (23) [M]+,
77 (100), 57 (34). IR (neat): ν = 3062, 2958, 2931, 2871, 2196, 1598,
˜
1573, 1490, 1446, 1318, 1151, 1086, 815, 756, 688 cm–1. C20H20O2S
(324.45): calcd. C 74.06, H 6.22; found C 73.81, H 6.34.
275 (58), 141 (100), 77 (38), 57 (44). IR (neat): ν = 2959, 2932, 2874,
˜
(E)-1-(Benzenesulfonyl)-2-butyl-5-hydroxypent-1-en-3-yne
(3c):
2215, 1579, 1447, 1308, 1149, 1086, 816, 755, 689 cm–1. C17H22O3S
(306.43): calcd. C 66.63, H 7.24; found C 66.41, H 6.98.
Yield: 2.42 g, 87%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.92–
7.89 (m, 2 H), 7.65–7.53 (m, 3 H), 6.52 (s, 1 H), 4.40 (s, 2 H), 2.68
(t, J = 7.6 Hz, 2 H), 1.68 (s, 1 H), 1.51–1.45 (m, 2 H), 1.36–1.31
(E)-1-(Benzenesulfonyl)-2-(2-methoxyethyl)-4-phenylbut-1-en-3-yne
(m, 2 H), 0.90 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, (3i): Yield: 2.84 g, 87%. Oil. 1H NMR (400 MHz, CDCl3): δ = 7.97
CDCl3): δ = 141.58, 140.38, 134.02, 133.54, 129.32 (2 C), 127.32 (2
(d, J = 8.4 Hz, 2 H), 7.64–7.54 (m, 3 H), 7.43 (d, J = 8.0 Hz, 2 H),
C), 94.75, 83.96, 51.17, 31.29, 30.24, 22.33, 13.79 ppm. MS (EI):
7.38–7.31 (m, 3 H), 6.67 (s, 1 H), 3.71–3.67 (m, 2 H), 3.35 (s, 3 H),
834
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 831–836

Stereoselective Synthesis of 1,3-Dienes Containing Tin and Sulfonyl Groups
3.14 (t, J = 6.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
141.39, 137.11, 134.65, 133.57, 131.99 (2 C), 129.65, 129.32 (2 C),
128.55 (2 C), 127.59 (2 C), 121.51, 97.05, 87.38, 70.27, 58.73,
(2 C), 127.69 (2 C), 127.32 (2 C), 124.52, 32.10 (3JSn,C = 56 Hz),
30.32, 28.71 (3 C), 27.20 (3 C), 22.56, 13.98, 13.64 (3 C), 10.15 (3
C) ppm. MS (EI): m/z (%) = 616 (2.3) [M]+, 559 (100), 291 (47),
31.59 ppm. MS (EI): m/z (%) = 326 (27) [M]+, 295 (100), 141 (56), 141 (36), 77 (81), 57 (64). IR (neat): ν = 3060, 2956, 2927, 2871,
˜
77 (65). IR (neat): ν = 3061, 2927, 2892, 2199, 1597, 1574, 1490, 1580, 1565, 1464, 1446, 1303, 1149, 1085, 689 cm–1. C32H48O2SSn
˜
1446, 1319, 1150, 1085, 816, 755, 688 cm–1. C19H18O3S (326.42):
calcd. C 69.91, H 5.56; found C 69.68, H 5.31.
(615.51): calcd. C 62.44, H 7.86; found C 62.15, H 7.67.
(1E,3E)-1-(Benzenesulfonyl)-2-(2-methoxyethyl)-3-(tributylstannyl)-
1
General Procedure for the Palladium-Catalyzed Hydrostannylation octa-1,3-diene (4e): Yield: 0.513 g, 86%. Oil. H NMR (400 MHz,
of (E)-1-Benzenesulfonyl-Substituted 1,3-Enynes: Enyne 3 CDCl3): δ = 7.94 (d, J = 8.4 Hz, 2 H), 7.58–7.49 (m, 3 H), 5.89 (s,
3
(1.0 mmol) was added dropwise to a solution prepared by adding
tributylstannane (1.1 mmol) to Pd(PPh3)4 (0.02 mmol) in THF
(2 mL) at room temperature under an argon atmosphere. After 4 h,
the reaction mixture was evaporated in vacuo, and the residue was
purified by column chromatography (light petroleum ether/diethyl
ether, 4:1) on silica gel.
1 H), 5.53 (t, J = 7.2, JSn,H = 56 Hz, 1 H), 3.37 (t, J = 6.8 Hz, 2
H), 3.27 (s, 3 H), 2.90 (t, J = 6.8 Hz, 2 H), 2.03–1.92 (m, 2 H),
1.43–1.15 (m, 16 H), 0.89–0.74 (m 18 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 160.68, 144.56, 143.04, 142.11, 132.77,
129.00 (2 C), 127.06 (2 C), 123.52, 69.90, 58.42, 31.84 (3JSn,C
=
55 Hz), 30.51, 28.91, 28.81 (3 C), 27.23 (3 C), 22.44, 13.95, 13.63
(3 C), 10.52 (3 C) ppm. MS (EI): m/z (%) = 598 (1.7) [M]+, 567
(1E,3E)-1-(Benzenesulfonyl)-2,4-dibutyl-3-(tributylstannyl)buta-1,3-
(46), 541 (100), 291 (29), 141 (35), 77 (32), 57 (47). IR (neat): ν =
˜
1
diene (4a): Yield: 0.541 g, 91%. Oil. H NMR (400 MHz, CDCl3):
3065, 2956, 2926, 2872, 1579, 1464, 1447, 1307, 1149, 1086,
689 cm–1. C29H50O3SSn (597.50): calcd. C 58.30, H 8.44; found C
58.49, H 8.26.
δ = 7.92 (d, J = 8.4 Hz, 2 H), 7.58–7.49 (m, 3 H), 5.87 (s, 1 H),
3
5.52 (t, J = 7.6, JSn,H = 56 Hz, 1 H), 2.52 (t, J = 7.2 Hz, 2 H),
2.06–1.98 (m, 2 H), 1.40–1.17 (m, 20 H), 0.91–0.73 (m, 21 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 164.29, 144.75, 143.49, 141.87,
(1E,3E)-1-(Benzenesulfonyl)-2-(2-methoxyethyl)-4-phenyl-3-(tribut-
ylstannyl)buta-1,3-diene (4f): Yield: 0.543 g, 88%. Oil. H NMR
132.68, 129.01 (2 C), 126.92 (2 C), 122.01, 31.95, 31.59 (3JSn,C
=
1
54 Hz), 30.59, 29.49, 28.83 (3 C), 27.24 (3 C), 23.04, 22.45, 13.97, (400 MHz, CDCl3): δ = 7.93 (d, J = 8.0 Hz, 2 H), 7.63–7.53 (m, 3
13.87, 13.63 (3 C), 10.47 (3 C) ppm. MS (EI): m/z (%) = 596 (2.1)
H), 7.14–7.06 (m, 5 H), 6.45 (s, 3JSn,H = 64 Hz, 1 H), 6.01 (s, 1 H),
3.40 (t, J = 6.8 Hz, 2 H), 3.17 (s, 3 H), 2.98 (t, J = 6.8 Hz, 2 H),
[M]+, 539 (61), 291 (45), 141 (67), 77 (36), 57 (100). IR (neat): ν =
˜
3065, 2957, 2928, 2872, 1577, 1465, 1446, 1316, 1146, 1086, 1.55–1.44 (m, 6 H), 1.36–1.27 (m, 6 H), 0.96 (t, J = 8.0 Hz, 6 H),
689 cm–1. C30H52O2SSn (595.52): calcd. C 60.51, H 8.80; found C
60.24, H 8.62.
0.89 (t, J = 7.2 Hz, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
161.97, 149.08, 142.47, 138.38 (3JSn,C = 21 Hz), 136.56, 132.85,
129.10 (2 C), 128.67 (2 C), 128.20 (2 C), 127.50, 127.33 (2 C),
123.39, 70.53, 58.25, 32.13, 28.85 (3 C), 27.30 (3 C), 13.64 (3 C),
11.12 (3 C) ppm. MS (EI): m/z (%) = 618 (1.2) [M]+, 561 (64), 291
(1E,3E)-1-(Benzenesulfonyl)-2-butyl-4-phenyl-3-(tributylstannyl)-
1
buta-1,3-diene (4b): Yield: 0.566 g, 92%. Oil. H NMR (400 MHz,
CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.56–7.45 (m, 3 H), 7.07–
(10), 269 (36), 186 (100), 155 (60), 128 (59), 57 (66). IR (neat): ν =
˜
3
7.04 (m, 5 H), 6.37 (s, JSn,H = 64 Hz, 1 H), 5.90 (s, 1 H), 2.57 (t,
3060, 2956, 2926, 2871, 1596, 1577, 1463, 1447, 1307, 1148, 1085,
689 cm–1. C31H46O3SSn (617.49): calcd. C 60.30, H 7.51; found C
60.08, H 7.23.
J = 7.6 Hz, 2 H), 1.46–1.17 (m, 16 H), 0.90 (t, J = 8.0 Hz, 6 H),
0.82 (t, J = 7.2 Hz, 9 H), 0.76 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 165.15, 149.12, 142.83, 138.23 (3JSn,C
=
23 Hz), 136.51, 132.77, 129.10 (2 C), 128.67 (2 C), 128.21 (2 C), General Procedure for the Stille Coupling of (1E,3E)-1-(Benzenesulf-
127.47, 127.17 (2 C), 121.93, 32.06, 30.38, 28.84 (3 C), 27.29 (3 C), onyl)-2,4-Dibutyl-3-(Tributylstannyl)Buta-1,3-diene 4a with Aryl
23.29, 13.73, 13.64 (3 C), 10.99 (3 C) ppm. MS (EI): m/z (%) = 616 Iodides: (1E,3E)-1-Benzenesulfonyl-2,4-dibutyl-3-(tributylstannyl)-
(1.4) [M]+, 559 (100), 291 (37), 141 (43), 77 (58), 57 (41). IR (neat):
buta-1,3-diene (4a, 1.0 mmol) and aryl iodide (1.1 mmol) were dis-
ν = 3059, 3023, 2957, 2928, 2871, 1596, 1577, 1464, 1447, 1316, solved in DMF (8 mL) under an atmosphere of argon at room
˜
1149, 1086, 689 cm–1. C32H48O2SSn (615.51): calcd. C 62.44, H
7.86; found C 62.56, H 7.62.
temperature. Pd(PPh3)4 (0.05 mmol) and CuI (0.75 mmol) were
then added. The mixture was stirred for 8 h at room temperature
and monitored by TLC (SiO2) for the disappearance of 4a. The
reaction mixture was diluted with diethyl ether (30 mL), filtered,
and then treated with 20% aqueous KF (10 mL) for 30 min before
being dried and concentrated. The residue was purified by column
chromatography (light petroleum ether/diethyl ether, 4:1) on silica
gel.
(1E,3E)-1-(Benzenesulfonyl)-2-butyl-5-hydroxy-3-(tributylstannyl)-
penta-1,3-diene (4c): Yield: 0.506 g, 89%. Oil. 1H NMR (400 MHz,
CDCl3): δ = 7.92–7.90 (m, 2 H), 7.59–7.51 (m, 3 H), 5.87 (s, 1 H),
3
5.75 (t, J = 6.4, JSn,H = 60 Hz, 1 H), 4.12 (t, J = 5.6 Hz, 2 H),
2.54 (t, J = 8.0 Hz, 2 H), 1.57 (s, 1 H), 1.44–1.19 (m, 16 H), 0.94–
0.78 (m 18 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 163.23,
148.13, 143.10, 139.39, 132.88, 129.12 (2 C), 126.93 (2 C), 122.08,
(1E,3E)-1-(Benzenesulfonyl)-2-butyl-3-phenylocta-1,3-diene (5a):
60.62 (3JSn,C = 46 Hz), 31.22, 29.59, 28.75 (3 C), 27.19 (3 C), 22.96, Yield: 0.302 g, 79%. Oil. 1H NMR (400 MHz, CDCl3): δ = 8.01
13.78, 13.55 (3 C), 10.58 (3 C) ppm. MS (EI): m/z (%) = 570 (1.1)
(d, J = 7.6 Hz, 2 H), 7.66–7.49 (m, 4 H), 7.28–7.16 (m, 4 H), 6.35
(s, 1 H), 5.87 (t, J = 7.6 Hz, 1 H), 2.57 (t, J = 7.2 Hz, 2 H), 2.11–
2.03 (m, 2 H), 1.38–1.16 (m, 8 H), 0.85 (t, J = 7.2 Hz, 3 H), 0.77
(t, J = 6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.55,
142.53, 140.38, 138.95, 133.31, 132.21, 129.91, 129.30 (2 C), 128.54
(2 C), 127.68, 127.20 (2 C), 126.60 (2 C), 32.08, 30.24, 29.56, 29.36,
22.82, 22.56, 14.01, 13.86 ppm. MS (EI): m/z (%) = 382 (27) [M]+,
[M]+, 513 (15), 269 (77), 81 (100), 77 (69), 57 (80). IR (neat): ν =
˜
3515, 3065, 2957, 2929, 2872, 1575, 1464, 1447, 1306, 1144, 1085,
689 cm–1. C27H46O3SSn (569.44): calcd. C 56.95, H 8.14; found C
56.68, H 7.89.
(1E,3E)-1-(Benzenesulfonyl)-2-phenyl-3-(tributylstannyl)octa-1,3-
1
diene (4d): Yield: 0.572 g, 93%. Oil. H NMR (400 MHz, CDCl3):
141 (100), 77 (61), 57 (54). IR (neat): ν = 3023, 2956, 2927, 2873,
˜
δ = 7.57 (d, J = 8.0 Hz, 2 H), 7.45 (t, J = 7.0 Hz, 1 H), 7.33–7.23
(m, 5 H), 7.15 (d, J = 7.6 Hz, 2 H), 6.24 (s, 1 H), 5.61 (t, J = 6.8,
3JSn,H = 56 Hz, 1 H), 2.18–2.09 (m, 2 H), 1.36–1.12 (m, 16 H),
0.90–0.76 (m 18 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 160.21,
145.46, 142.36, 141.76, 135.38, 132.51, 129.07, 129.01 (2 C), 128.51
1608, 1505, 1464, 1443, 1312, 1147, 1085, 689 cm–1. C24H30O2S
(382.57): calcd. C 75.35, H 7.90; found C 75.07, H 7.75.
(1E,3E)-1-(Benzenesulfonyl)-2-butyl-3-(4-methoxyphenyl)octa-1,3-
1
diene (5b): Yield: 0.322 g, 78%. Oil. H NMR (400 MHz, CDCl3):
Eur. J. Org. Chem. 2012, 831–836
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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835

H. Zhao, W. Yang, S. Xie, M. Cai
FULL PAPER
[6] a) J. E. Bäckvall, A. Ericsson, J. Org. Chem. 1994, 59, 5850–
5851; b) T. G. Back, S. Collins, J. Org. Chem. 1981, 46, 3249–
3256; c) Y. Chen, J. B. Evarts, E. Torres, P. L. Fuchs, Org. Lett.
2002, 4, 3571–3574.
δ = 8.00 (d, J = 7.6 Hz, 2 H), 7.65–7.58 (m, 3 H), 7.09 (d, J =
8.4 Hz, 2 H), 6.80 (d, J = 8.4 Hz, 2 H), 6.32 (s, 1 H), 5.77 (t, J =
7.6 Hz, 1 H), 3.79 (s, 3 H), 2.57 (t, J = 7.6 Hz, 2 H), 2.08–1.97 (m,
2 H), 1.33–1.13 (m, 8 H), 0.85 (t, J = 7.0 Hz, 3 H), 0.77 (t, J =
6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 159.19,
157.79, 142.65, 139.92, 133.22, 131.56, 130.58, 129.63, 129.24 (2 C),
127.76 (2 C), 127.19 (2 C), 113.86 (2 C), 55.30, 32.17, 30.24, 29.47,
29.36, 22.82, 22.51, 13.97, 13.81 ppm. MS (EI): m/z (%) = 412 (8.3)
[7] a) K. Banert, W. Fendel, J. Schlott, Angew. Chem. 1998, 110,
3488; Angew. Chem. Int. Ed. 1998, 37, 3289–3292; b) C. Wang,
Q. Song, Z. Xi, Tetrahedron 2004, 60, 5207–5214; c) K. Banert,
J. Schlott, Tetrahedron 2000, 56, 5413–5419; d) J. W. Herndon,
P. P. Patel, J. Org. Chem. 1996, 61, 4500–4501; e) G. Desur-
mont, S. Dalton, D. M. Giolando, M. Srebnik, J. Org. Chem.
1996, 61, 7943–7946; f) B. H. Lipshutz, J. I. Lee, Tetrahedron
Lett. 1991, 32, 7211–7214; g) F. Babudri, G. M. Farinola, F.
Naso, R. Ragni, G. Spina, Synthesis 2007, 3088–3092.
[8] S. Massaki, K. Takuya, H. Tamejiro, Synlett 2001, 1006–1008.
[9] J.-H. Li, Y. Liang, Y.-X. Xie, J. Org. Chem. 2004, 69, 8125–
8127.
[M]+, 271 (37), 123 (93), 91 (47), 77 (100), 57 (54). IR (neat): ν =
˜
2958, 2926, 2874, 1607, 1510, 1465, 1446, 1306, 1249, 1150, 1086,
689 cm–1. C25H32O3S (412.60): calcd. C 72.78, H 7.82; found C
72.51, H 7.55.
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the NMR and mass spectra.
[10] M. Yoshimatsu, J. Hasegawa, J. Chem. Soc. Perkin Trans. 1
1997, 211–215.
[11] X. Huang, M. Xie, Org. Lett. 2002, 4, 1331–1334.
[12] F. Babudri, V. Fiandanese, L. Mazzone, F. Naso, Tetrahedron
Lett. 1994, 35, 8847–8850.
[13] M. C. Bernabeu, R. Chinchilla, C. Nájera, Tetrahedron Lett.
1995, 36, 3901–3904.
[14] T. G. Back, E. K. Y. Lai, K. R. Muralidharan, J. Org. Chem.
1990, 55, 4595–4602.
Acknowledgments
We thank the National Natural Science Foundation of China (Pro-
ject No. 20862008) and the Natural Science Foundation of Jiangxi
Province in China (2010GZH0062) for financial support.
[15] A. Padwa, Y. Gareau, B. Harrison, A. Rodriguez, J. Org. Chem.
1992, 57, 3540–3545.
[1] a) B. M. Trost, W. C. Vladuchick, A. J. Bridges, J. Am. Chem.
Soc. 1980, 102, 3554–3572; b) A. Padwa, B. H. Norman, Tetra-
hedron Lett. 1988, 29, 2417–2420; c) A. Padwa, B. Harrison,
S. S. Murphree, P. E. Yeske, J. Org. Chem. 1989, 54, 4232–4235;
d) M. Yoshimatsu, J. Hasegawa, J. Chem. Soc. Perkin Trans. 1
1997, 211–215; e) M. C. Aversa, A. Barattucci, P. Bonaccorsi,
P. Giannetto, D. N. Jones, J. Org. Chem. 1997, 62, 4376–4384.
[2] a) F. Naso, Pure Appl. Chem. 1988, 60, 79–88; b) W. H. Pear-
son, K.-C. Lin, Y.-F. Poon, J. Org. Chem. 1989, 54, 5814–5819;
c) P. A. Grieco, S. A. May, M. D. Kaufman, Tetrahedron Lett.
1998, 39, 7047–7050; d) M. Cai, D. Wang, P. Wang, J. Or-
ganomet. Chem. 2006, 691, 737–741.
[3] a) J. V. Camasseto, C. A. Brandt, Synthesis 1987, 146–148; b)
L. Hevesi, B. Hermans, C. Allard, Tetrahedron Lett. 1994, 35,
6729–6732; c) L. S. Zhu, Z. Z. Huang, X. Huang, Tetrahedron
1996, 52, 9819–9822; d) Y. Ma, X. Huang, J. Chem. Soc. Perkin
Trans. 1 1997, 2953–2955.
[16] M. Su, Y. Kang, W. Yu, Z. Hua, Z. Jin, Org. Lett. 2002, 4,
691–694.
[17] R. S. Coleman, M. C. Walczak, Org. Lett. 2005, 7, 2289–2292.
[18] M. Z. Cai, Z. Zhou, P. P. Wang, Synthesis 2006, 789–792.
[19] M. Z. Cai, Y. Wang, P. P. Wang, J. Organomet. Chem. 2008,
693, 2954–2958.
[20] B. M. Trost, C.-J. Li, Synthesis 1994, 1267–1270.
[21] a) H. X. Zhang, F. Guibe, G. Balavoine, J. Org. Chem. 1990,
55, 1857–1867; b) N. D. Smith, J. Mancuso, M. Lautens, Chem.
Rev. 2000, 100, 3257–3282.
[22] M. Alami, F. Ferri, Synlett 1996, 755–756.
[23] F. Ferri, M. Alami, Tetrahedron Lett. 1996, 37, 7971–7974.
[24] M. Cai, G. Chen, W. Hao, D. Wang, Synlett 2006, 3492–3494.
[25] A. J. Leusink, H. A. Budding, J. W. Marsman, J. Organomet.
Chem. 1967, 9, 285–294.
[26] J.-F. Betzer, P. Le Menez, J. Prunet, J.-D. Brion, J. Ardisson, A.
Pancrazi, Synlett 2002, 1–4.
[4] a) E. Negishi, F. T. Luo, J. Org. Chem. 1983, 48, 1560–1562; b)
T.-Y. Luh, K.-T. Wong, Synthesis 1993, 349–370; c) Z.-J. Ni,
P.-F. Yang, D. K. P. Ng, Y.-L. Tzeng, T.-Y. Luh, J. Am. Chem.
Soc. 1990, 112, 9356–9364.
[27] N. Greeves, J. S. Torode, Synlett 1994, 537–538.
[28] V. Gevorgyan, J. X. Liu, Y. Yamamoto, J. Org. Chem. 1997, 62,
2963–2967.
[5] a) F. Suzenet, E. Blart, J. P. Quintard, Synlett 1998, 879–881; [29] M. Lautens, C. Meyer, A. Lorenz, J. Am. Chem. Soc. 1996,
b) B. H. Lipshutz, C. Lindsley, J. Am. Chem. Soc. 1997, 119,
4555–4556; c) J. F. Betzer, F. Delaloge, B. Muller, A. Pancrazi,
J. Prunet, J. Org. Chem. 1997, 62, 7768–7780.
118, 10676–10677.
Received: August 5, 2011
Published Online: December 7, 2011
836
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 831–836