O-Benzenedisulfonimide as a reusable broonsted acid catalyst for hosomi-sakurai reactions

Article abstract of DOI:10.1055/s-0029-1217093

Various acetals or alcohols react with allyl(trimethyl)silane or 1-phenyl-2-(trimethylsilyl)acetylene in the presence of a catalytic amount of the Bronsted acid o-benzenedisulfonimide under mild conditions to give good yields of the corresponding products. The catalyst can be easily recovered and purified for use in further reactions, which has economic and ecological advantages. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-0029-1217093

PAPER
315
o-Benzenedisulfonimide as a Reusable Brønsted Acid Catalyst for
Hosomi–Sakurai Reactions
Reusable Catalyst
for
H
a
osomi–Sa
r
i
Re
g
a
ctions herita Barbero, Stefano Bazzi, Silvano Cadamuro, Stefano Dughera,* Claudia Piccinini
Dipartimento di Chimica Generale e Chimica Organica, Università di Torino, C.so Massimo d’Azeglio 48, 10125 Torino, Italy
Fax +39(011)6707642; E-mail: stefano.dughera@unito.it
Received 3 September 2009; revised 9 September 2009
First, we studied the reactions between acetals 2a–g or
ketal 2h with silane 3 (Scheme 1) in the presence of 1 (5
or 10 mol%); the results are listed in Table 1. We obtained
the corresponding homoallylic ethers 4a–h in good yields
Abstract: Various acetals or alcohols react with allyl(trimethyl)si-
lane or 1-phenyl-2-(trimethylsilyl)acetylene in the presence of a
catalytic amount of the Brønsted acid o-benzenedisulfonimide un-
der mild conditions to give good yields of the corresponding prod-
ucts. The catalyst can be easily recovered and purified for use in under simple and mild conditions. The products are useful
as intermediates in organic synthesis,10 or as precursors of
further reactions, which has economic and ecological advantages.
molecules with biological activity.11 Note also that the re-
Key words: homogeneous catalysis, Brønsted acid, Hosomi–
Sakurai reaction, acetals, alcohols
actions were carried out under solvent-free conditions,
which has economic and ecological benefits. Moreover,
the reaction was chemoselective; in entry 5, only traces of
diallylated product were detected. Furthermore, 1 could
be recovered in good yield (85%) simply by evaporating
the aqueous layer under reduced pressure and washing, as
reported below.
We have recently reported the use of o-benzenedisulfon-
imide (1, 1,3,2-benzodithiazole 1,1,3,3-tetraoxide;
Figure 1) in catalytic amounts as a safe, nonvolatile, and
noncorrosive Brønsted acid in some acid-catalyzed organ-
ic reactions, such as etherifications,1 esterifications,1,2
acetalizations,1 Ritter reactions,3 Nazarov electrocycliza-
tions,4 and disproportionations of dialkyl diarylmethyl
ethers5 under very mild and selective conditions. The cat-
alyst can be easily recovered and purified for use in fur-
ther reactions, which has economic and ecological
advantages.
OMe
1 (cat.)
TMS
+
R
OMe
R
OMe
X
X
2
4
3
Scheme 1 Hosomi–Sakurai reactions of acetals 2 with allyl(tri-
methyl)silane (3)
SO2
NH
SO2
1
When the reaction was carried out with silane 5
(Scheme 1), the yields of products 6a–d were fairly good
(Table 2); however, it was necessary to use a larger
amount of 1 (20 or 30 mol%) in acetonitrile as a solvent.
Compounds 6 are interesting building blocks for use in
Figure 1 o-Benzenedisulfonimide (1)
The Hosomi–Sakurai reaction6,7 generally involves the natural product synthesis;8a,c furthermore, some diaryl-
Lewis acid-promoted allylation of various electrophiles substituted propynyl compounds are useful in the treat-
with allyl(trimethyl)silane; in rare instances, other silanes ment of disorders of cell differentiation, proliferation, and
are used.8 Surprisingly, the use of Brønsted acids in im- keratinization.12
portant reaction has only been reported in a few recent pa-
pers.9 In the most significant of these,9e List describes the
Ph
Hosomi–Sakurai allylation of both aromatic and aliphatic
acetals in the presence of catalytic amount of six different
OMe
1 (cat.)
+
Ph
TMS
Brønsted acids, the best results being obtained with 2,4-
dinitrobenzenesulfonic acid.
MeCN, 80 °C
R
OMe
R
OMe
H
H
2
6
5
We have found that the Hosomi–Sakurai reaction of two
different classes of electrophiles, namely acetals or ketals
2 and alcohols 11, with allyl(trimethyl)silane (3) or 1-phe-
nyl-2-(trimethylsilyl)acetylene (5) takes place in the pres-
ence of 1 as a catalyst.
Scheme 2 Hosomi–Sakurai reactions of acetals 2 with 1-phenyl-2-
(trimethylsilyl)acetylene (5)
It was possible to reuse the recovered 1 in several consec-
utive runs without a significant loss of catalytic activity or
a decrease in the yield of 4a (Table 3).
SYNTHESIS 2010, No. 2, pp 0315–0319
x
x
.
x
x
.2
0
0
9
Advanced online publication: 03.11.2009
DOI: 10.1055/s-0029-1217093; Art ID: Z18509SS
© Georg Thieme Verlag Stuttgart · New York

316
M. Barbero et al.
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Table 1 Hosomi–Sakurai Reactions of Acetals 2a–g or Ketal 2h with Allyl(trimethyl)silane (3)
Entry
Acetal/ketal
R
X
H
H
H
H
H
H
H
Me
Ratio 2/3 Catalyst 1 (mol%) Temp (°C) Time (h)
Product
4a
Yielda (%)
1
2
3
4
5
6
7
8
2a
2b
2c
2d
2e
2f
Ph
1:1.2
1:1.2
1:1.2
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
5
45
45
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
2
90
4-MeOC6H4
5
2.5
3
4b
88
4-O2NC6H4
5
4c
88
(CH2)4Me
10
10
10
10
10
2.5
1
4d
90
(E)-CH2CH=CHMe
4e
72b
81
Cy
Bn
Ph
1.5
8
4f
2g
2h
4g
91c
79c
24
4h
a Yield of pure product.
b 4e was purified by flash chromatography (PE–Et2O, 9.8:0.2). In the GC/MS analyses of the crude residue, weak traces of diallylated product,
MS (EI, 70 eV): m/z 155 (8) [M+ – 41], were detected.
c The products were purified by flash chromatography on a short column (PE–Et2O, 9.8:0.2).
Table 2 Hosomi–Sakurai Reactions of Acetals 2a–d with 1-Phenyl-2-(trimethylsilyl)acetylene (5)
Entry
Acetal
2a
R
Ratio 2/5
1:1.5
Catalyst 1 (mol%)
Time (h)
Product
6a
Yielda (%)
1
2
3
4
Ph
20
30
30
30
7
65
65
54
55
2b
4-MeOC6H4
4-O2NC6H4
(CH2)4Me
1:1.5
8
6b
2c
1:1.5
8
6c
2d
1:1.5
4.5
6d
a Yield of pure product obtained by flash chromatography on a short column (PE–Et2O, 9.8:0.2).
Table 3 Consecutive Reactions with Recycled Catalyst 1
but could not be isolated because of its volatility. In light
of this, the silane 5 reacts less readily because, instead of
the stable carbocation 8, a less-stable vinylic carbocation
is formed.
Entry
Yielda (%) of 4a
Recovery of 1
85% (94 mg)c
80% (75 mg)e
75% (56 mg)
1
2
3
90b
85d
85f
MeOTMS
10
2
Z-H
1
a Yields refer to the pure product; the reaction time was 2 hours for all
the reactions.
MeOH
MeOH
b The reaction was performed with 10 mmol of 2a (1.52 g) and 5
mol% of 1 (0.11 g, 0.5 mmol).
Z
OMe
Z
TMS
R
7
c The recovered 1 (94 mg) was reused in entry 2.
d The reaction was performed with 8.58 mmol of 2a (1.30 g) and 5
mol% of 1 (94 mg, 0.429 mmol).
9
3
4
OMe
e The recovered 1 (75 mg) was reused in entry 3.
f The reaction was performed with 6.84 mmol of 2a (1.04 g) and 5
mol% of 1 (75 mg, 0.342 mmol).
TMS
R
8
Z
SO2
= Z-H
NH
SO2
As reported by List,9e the reaction can be described by a
catalytic cycle (Scheme 3), in which 1 is regenerated by
the reaction of the intermediate 9 with methanol (or water
in the case of the reactions shown below in Scheme 4). It
must be stressed that no traces of 9 were detected; on the
contrary, product 10 was identified by GC-MS analysis,
Scheme 3 Catalytic cycle
To further explore the synthetic usefulness of o-benzene-
disulfonimide (1) in Hosomi–Sakurai reactions, we also
studied the reactions between alcohols 11a–h and silane 3
Synthesis 2010, No. 2, 315–319 © Thieme Stuttgart · New York

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Reusable Catalyst for Hosomi–Sakurai Reactions
317
Table 4 Hosomi–Sakurai Reactions of Alcohols 11
Entry
Alcohol
11a
Ar
X
H
H
H
H
H
H
H
Ph
R
Catalyst 1 (mol%)a
Time (h)
24
Temp (°C)
Product
12a
Yieldb (%)
1
2
3
4
5
6
7
8
Ph
Me
30
30
5
70
70
r.t.
r.t.
r.t.
r.t.
70
r.t.
72c
75d
91
11b
11c
Ph
Ph
24
12b
12c
Ph
2-HOC6H4
Ph
0.25
0.25
0.25
1
11d
11e
4-MeOC6H4
4-MeOC6H4
4-Me2NC6H4
4-FC6H4
Ph
5
12d
12e
93
4-MeOC6H4
4-Me2NC6H4
4-FC6H4
Ph
5
95
11f
5
12f
92
11g
30
5
24
12g
74e
95
11h
0.25
12h
a The reactants ratio was 11/3 = 1:1.5.
b Yield of pure product.
c 12a was purified by flash chromatography (PE–Et2O, 9.8:0.2). In the GC/MS analyses of the crude residue, weak traces of styrene, MS (EI,
70 eV): m/z = 104 (100) [M]+ and bis(1-phenylethyl) ether, MS (EI, 70 eV): m/z = 226 (54) [M]+, 105 (100), were detected.
d 12b was purified by flash chromatography (PE–Et2O, 9.8:0.2). In the GC/MS analyses of the crude residue, weak traces of bis(diphenyl-
methyl)ether, MS (EI, 70 eV): m/z = 350 (34) [M]+, 167 (100) were detected.
e 12g was purified by flash chromatography (PE–Et2O, 9.8:0.2). In the GC/MS analyses of the crude residue, weak traces of bis[bis(4-fluoro-
phenyl)methyl)] ether, MS (EI, 70 eV): m/z = 422 (4) [M]+, 203 (100) were detected.
in the presence of 1 as a catalyst (Scheme 4). The results noncorrosive Brønsted acid; 2) it is readily recovered at
are reported in Table 4. We obtained excellent results with the end of the reactions simply by evaporating the aque-
diarylmethanols 11c–f (entries 3–6) bearing one or two ous washings; 3) the target products 4, 6, and 12 are gen-
electron-donating groups, and with triphenylmethanol erally obtained in excellent yields under simple and mild
(11h; entry 8); these reactions took place rapidly under reaction conditions; and 4) the reactions are usually car-
solvent-free conditions, and it was necessary to use only 5 ried out under solvent-free conditions, with consequent
mol% of 1. With 11a, 11b, and 11g, (entries 1, 2, and 7, economic and ecological benefits.
respectively), which do not contain strong electron-donat-
ing groups, we obtained lower yields of products 6, and
All the reactions were conducted in open flasks. Analytical grade
harsher reaction conditions were required. The greater sta-
bility of the cations arising from 11c–f and 11h facilitates
the reaction significantly.
reagents and solvents were used and the reactions were monitored
by TLC, GC, and GC-MS. Flash chromatography was carried out
on silica gel (particle size 0.032–0.063 mm). Petroleum ether (PE)
1
refers to the fraction boiling in the range 40–70 °C. H NMR and
13C NMR were recorded on a Bruker Avance 200 spectrometer at
200 and 50 MHz, respectively. Mass spectra were recorded on an
HP 5989B mass-selective detector connected to an HP 5890 GC.
The room temperature was 20–25 °C. o-Benzenedisulfonimide
(1),15 acetals 2c, 2e, 2f,16 and alcohols 11c and 11f17 were prepared
as reported in the literature; all the other reactants were purchased
OH
1 (cat.)
+ 3
Ar
R
Ar
R
X
X
12
11
1
from Sigma-Aldrich. Yields of the pure (GC, GC-MS, TLC, H
NMR, 13C NMR) isolated products 4, 6, and 12 are reported in
Tables 1, 2, and 3 respectively. Structures and purity of the products
4a,18 4b,18 4f,19 4g,20 6a,21 6b,22 12a,13 12b,13 12d,23 12e,13 12g24,
and 12h13 were confirmed by comparison of their physical and spec-
tral data with those reported in the literature. Products 4c,9e 4h,9e
12c,14b and 12f25 are known in the literature, but no physical and
spectral data have been reported. Satisfactory microanalyses were
obtained for the new compounds 4d, 4e, 6c, and 6d.
Scheme 4 Hosomi–Sakurai reactions of alcohols 11
Several reactions between various alcohols and silyl com-
pounds in the presence of Lewis acids7i,l,m,8a,c,13 or the
Brønsted acid bis(fluorosulfuryl)imide9a as catalysts are
known. However, most of these reactions require the use
of environmentally dangerous halogenated solvents or
neurotoxic hexane.
(1-Methoxybut-3-en-1-yl)benzene (4a); Typical Procedure
o-Benzenedisulfonimide (1; 0.11 g, 0.5 mmol; 5 mol%) was added
to a mixture of acetal 2a (1.52 g, 10 mmol) and allyl(trimethyl)si-
lane (3, 1.37 g, 12 mmol), and the mixture was stirred at 45 °C. The
reaction was monitored by TLC, GC, and GC-MS until 2a com-
pletely disappeared (2 h). On GC-MS analysis, besides 4a [MS (EI,
70 eV): m/z (%) = 162 (2) [M+], 121 (100)], methoxy(trimethyl)si-
lane (10) [MS (EI, 70 eV): m/z (%) = 104 (2) [M+], 89 (100)], was
It must be stressed that some compounds 12, in particular
12c,14a–c are important precursors of molecules that show
interesting biological activities.14
In conclusion, the advantages of performing the Hosomi–
Sakurai reactions in the presence of 1 as catalyst can be
summarized as follows: 1) it is a safe, nonvolatile, and
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318
M. Barbero et al.
PAPER
detected, but this could not be isolated owing to its volatility. The
mixture was poured into Et2O–H2O (1:1; 100 mL), and the aqueous
layer was separated and extracted with Et2O (2 × 50 mL). The com-
bined organic extracts were washed with H2O (2 × 50 mL), dried
(Na2SO4), and concentrated under reduced pressure. The crude res-
idue was the virtually pure (GC, GC-MS, TLC, 1H NMR, 13C NMR)
4a, obtained as a yellow viscous oil; yield: 1.46 g (90%). The aque-
ous layer and aqueous washings were collected and evaporated un-
der reduced pressure. After removal of the water, virtually pure (1H
NMR), o-benzenedisulfonimide (1) was recovered (94 mg, 85%
yield). The recovered 1 was employed in other two catalytic cycles
under the conditions described above.
(2-Methoxypent-4-en-2-yl)benzene (4h)
Yellow viscous oil; yield: 1.39 g (79%) from 2h (1.66 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1H NMR (200 MHz, CDCl3): d = 1.55 (s, 3 H), 2.56 (d, J = 1.4 Hz,
2 H), 3.11 (s, 3 H), 5.00–5.08 (m, 2 H), 5.58–5.78 (m, 1 H), 7.27–
7.40 (m, 5 H).
13C NMR (50 MHz, CDCl3): d = 22.6, 47.1, 50.2, 78.5, 117.4,
126.1, 126.7, 127.9, 133.9, 146.1.
MS (EI, 70 eV): m/z (%) = 161 (2) [M+ – 15], 135 (100).
1,1¢-(3-Methoxyprop-1-yne-1,3-diyl)dibenzene (6a)
Yellow viscous oil; yield: 1.45 g (65%) from 2a (1.52 g, 10 mmol)
and 5 (2.61 g, 15 mmol).
Products 6 were synthesized in the same conditions as compounds
4, the only difference being that of MeCN (5 mL) was added as a
solvent.
1-Methoxy-4-(1-methoxy-3-phenylprop-2-yn-1-yl)benzene (6b)
Yellow viscous oil; yield: 1.65 g (65%) from 2b (1.82 g, 10 mmol)
and 5 (2.61 g, 15 mmol).
1-Methoxy-4-(1-methoxybut-3-en-1-yl)benzene (4b)
Yellow viscous oil; yield: 1.69 g (88%) from 2b (1.82 g, 10 mmol)
and 3 (1.37 g, 12 mmol).
1-(1-Methoxy-3-phenylprop-2-yn-1-yl)-4-nitrobenzene (6c)
Yellow viscous oil; yield: 1.44 g (54%) from 2c (1.97 g, 10 mmol)
and 5 (2.61 g, 15 mmol).
1H NMR (200 MHz, CDCl3): d = 3.56 (s, 3 H), 5.40 (s, 1 H), 7.33–
7.37 (m, 3 H), 7.47–7.52 (m, 2 H), 7.76 (d, J = 8.8 Hz, 2 H), 8.26
(d, J = 8.8 Hz, 2 H).
13C NMR (50 MHz, CDCl3): d = 54.4, 73.1, 86.2, 88.8, 122.4,
123.2, 128.4, 128.6, 132.6, 145.3, 148.2.
MS (EI, 70 eV): m/z (%) = 267 (25) [M+], 236 (100).
1-(1-Methoxybut-3-en-1-yl)-4-nitrobenzene (4c)
Yellow viscous oil; yield: 1.83 g (88%) from 2c (1.97 g, 10 mmol)
and 3 (1.37 g, 12 mmol).
1H NMR (200 MHz, CDCl3): d = 2.39–2.57 (m, 2 H), 3.33 (s, 3 H),
4.35–4.42 (m, 1 H), 4.97–5.06 (m, 2 H), 5.62–5.85 (m, 1 H), 7.47
(d, J = 8.8 Hz, 2 H), 8.20 (d, J = 8.8 Hz, 2 H).
13C NMR (50 MHz, CDCl3): d = 42.1, 64.5, 80.6, 117.3, 123.3,
127.1, 133.5, 147.0, 150.0.
MS (EI, 70 eV): m/z (%) = 207 (2) [M+], 166 (100).
Anal. Calcd for C16H13NO3: C, 71.90; H, 4.90; N, 5.24. Found: C,
71.95; H, 4.84; N, 5.31.
4-Methoxynon-1-ene (4d)
Yellow viscous oil; yield: 1.40 g (90%) from 2d (1.46 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1H NMR (200 MHz, CDCl3): d = 0.86 (t, J = 6.6 Hz, 3 H), 1.29–
1.45 (m, 8 H), 2.20–2.27 (m, 2 H) 3.15–3.21 (m, 1 H), 3.31 (s, 3 H),
5.00–5.11 (m, 2 H), 5.75–5.86 (m, 1 H).
13C NMR (50 MHz, CDCl3): d = 13.8, 22.4, 24.7, 31.8, 33.1, 37.6,
56.3, 80.3, 116.5, 134.8.
MS (EI, 70 eV): m/z (%) = 115 (80) [M+ – 41], 83 (100).
(3-Methoxyoct-1-yn-1-yl)benzene (6d)
Yellow viscous oil; yield: 1.18 g (55%) from 2d (1.46 g, 10 mmol)
and 5 (2.61 g, 15 mmol).
1H NMR (200 MHz, CDCl3): d = 0.92 (t, J = 6.6 Hz, 3 H), 1.27–138
(m, 6 H), 1.79–1.86 (m, 2 H), 3.45 (s, 3 H), 4.18 (t, J = 6.2 Hz, 1 H),
7.30–7.34 (m, 3 H), 7.44–7.46 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 13.8, 22.4, 24.8, 32.4, 35.5, 56.3,
71.6, 86.1, 88.0, 122.5, 128.0, 128.2, 131.5.
MS (EI, 70 eV): m/z (%) = 216 (2) [M+], 145 (100).
Anal. Calcd for C10H20O: C, 76.86; H, 12.90. Found: C, 76.82; H,
12.88.
Anal. Calcd for C15H20O: C, 83.29; H, 9.32. Found: C, 83.32; H,
9.38.
(7E)-4-Methoxynona-1,7-diene (4e)
Yellow viscous oil; yield: 1.11 g (72%) from 2e (1.44 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1,1¢-But-1-ene-4,4-diylbis(4-methoxybenzene) (12e); Typical
Procedure
1H NMR (200 MHz, CDCl3): d = 0.88 (t, J = 6.6 Hz, 3 H), 1.44–
1.50 (m, 2 H), 1.98–2.08 (m, 2 H), 2.20–2.27 (m, 2 H), 3.28–3.36
(m, 1 H), 3.51 (s, 3 H), 5.00–5.11 (m, 2 H), 5.28–5.35 (m, 1 H),
5.52–5.58 (m, 1 H), 5.75–5.88 (m, 1 H).
13C NMR (50 MHz, CDCl3): d = 18.6, 26.8, 35.9, 38.8, 56.2, 81.5,
114.7, 124.1, 131.5, 136.5.
o-Benzenedisulfonimide (1; 0.11 g, 0.5 mmol; 5 mol%) was added
to a mixture of alcoho 11e (2.44 g, 10 mmol) and allyl(trimethyl)si-
lane (3, 1.71 g, 15 mmol), and the mixture was stirred at r.t. for 15
min. The crude residue consisted of virtually pure (GC, GC-MS,
TLC, 1H NMR, 13C NMR) compound 12e, waxy solid; yield: 2.55
g (95%). o-Benzenedisulfonimide (1) was also recovered (98 mg,
89% yield).
MS (EI, 70 eV): m/z (%) = 113 (55) [M+ – 41], 57 (100).
Pent-4-en-2-ylbenzene (12a)
Yellow viscous oil; yield: 1.05 g (72%) from 11a (1.22 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
Anal. Calcd for C10H18O: C, 77.87; H, 11.76. Found: C, 77.83; H,
11.81.
(1-Methoxybut-3-en-1-yl)cyclohexane (4f)
Yellow viscous oil; yield: 1.36 g (81%) from 2f (1.58 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1,1¢-But-1-ene-4,4-diyldibenzene (12b)
Yellow viscous oil; yield: 1.55 g (75%) from 11b (1.84 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
(2-Methoxypent-4-en-1-yl)benzene (4g)
Yellow viscous oil; yield: 1.61 g (91%) from 2g (1.66 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
2-(1-Phenylbut-3-en-1-yl)phenol (12c)
Yellow viscous oil; yield: 1.05 g (91%) from 11c (2.04 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
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Reusable Catalyst for Hosomi–Sakurai Reactions
319
1H NMR (200 MHz, CDCl3): d = 2.75–2.87 (m, 2 H), 4.07–4.13 (t,
J = 6.2 Hz, 1 H), 5.05–5.20 (m, 2 H), 5.78–5.96 (m, 1 H), 6.73–6.85
(m, 2 H), 7.02–7.30 (m, 7 H).
J.-X. Synth. Commun. 2008, 38, 1011. (g) Shizuka, M.;
Snapper, M. L. Angew. Chem. Int. Ed. 2008, 47, 5049.
(h) Das, B.; Damodar, K.; Saritha, D.; Chowdhury, N.;
Krishnaiah, M. Tetrahedron Lett. 2007, 48, 7930. (i) Saito,
T.; Nishimoto, Y.; Yasuda, M.; Baba, A. J. Org. Chem.
2006, 71, 8516. (j) Ollevier, T.; Li, Z. Org. Biomol. Chem.
2006, 4, 4440. (k) Sellars, J. D.; Steel, P. G.; Turner, M. J.
Chem. Commun. 2006, 2385. (l) Kabalka, G. W.; Yao,
M.-L.; Borella, S. J. Am. Chem. Soc. 2006, 128, 11320.
(m) Nishibayashi, Y.; Shinoda, A.; Miyake, Y.; Matsuzawa,
H.; Sato, M. Angew. Chem. Int. Ed. 2006, 45, 4835.
(n) Wadamoto, M.; Yamamoto, Y. J. Am. Chem. Soc. 2005,
127, 14556.
13C NMR (50 MHz, CDCl3): d = 41.5, 53.3, 114.0, 116.7, 122.3,
126.5, 127.8, 128.4, 129.1, 129.5, 133.5, 135.6, 144.3, 154.1.
MS (EI, 70 eV): m/z (%) = 224 (2) [M+], 183 (100).
1-Methoxy-4-(1-phenylbut-3-en-1-yl)benzene (12d)
Yield: 2.21 g (93%) from 11d (2.14 g, 10 mmol) and 3 (1.71 g, 15
mmol); mp 44–45 °C (MeOH).
4,4¢-But-1-ene-4,4-diylbis(N,N-dimethylaniline) (12f)
Yellow viscous oil; yield: 2.71 g (92%) from 11f (2.70 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1H NMR (200 MHz, CDCl3): d = 2.85 (s, 6 H), 2.90–2.97 (m, 2 H),
4.08–4.15 (t, J = 6.2 Hz, 1 H), 5.07–5.22 (m, 2 H), 5.75–6.00 (m, 1
H), 6.72 (d, J = 8.8 Hz, 2 H), 6.94 (d, J = 8.8 Hz, 2 H).
13C NMR (50 MHz, CDCl3): d = 39.9, 40.1, 50.3, 113.8, 116.2,
129.1, 132.8, 136.6, 146.2.
MS (EI, 70 eV): m/z (%) = 294 (2) [M+], 253 (100).
(8) For some examples, see: (a) Hayashi, M.; Inubushi, A.;
Mukaiyama, T. Bull. Chem. Soc. Jpn. 1988, 61, 4037.
(b) Yadav, J. S.; Reddy, B. V. S.; Sridhar Reddy, M.;
Parimala, G. Synthesis 2003, 2390. (c) Sanz, R.; Martínez,
A.; Alvarez-Gutiérrez, J. M.; Rodríguez, F. Eur. J. Org.
Chem. 2006, 1383.
(9) (a) Kaur, G.; Kaushik, M.; Trehan, S. Tetrahedron Lett.
1997, 14, 2521. (b) Ishihara, K.; Hasegawa, A.; Yamamoto,
H. Angew. Chem. Int. Ed. 2001, 40, 4077. (c) Ishihara, K.;
Hiraiwa, H.; Yamamoto, H. Synlett 2001, 1851.
(d) Ishihara, K.; Hasegawa, A.; Yamamoto, H. Synlett 2002,
1299. (e) Kampen, D.; List, B. Synlett 2006, 2589.
(f) Kampen, D.; Ladépêche, A.; Claßen, G.; List, B. Adv.
Synth. Catal. 2008, 350, 962.
1,1¢-But-1-ene-4,4-diylbis(4-fluorobenzene) (12g)
Yellow viscous oil; yield: 1.80 g (74%) from 11g (2.20 g, 10 mmol)
and 3 (1.71 g, 15 mmol).
1,1¢,1¢¢-But-1-ene-4,4,4-triyltribenzene (12h)
Yield: 2.69 g (95%) from 11h (2.60 g, 10 mmol) and 3 (1.71 g, 15
mmol); mp 70–71 °C (MeOH).
(10) (a) Spafford, M. J.; Anderson, E. D.; Lacey, J. R.; Palma, A.
C.; Mohan, R. S. Tetrahedron Lett. 2007, 48, 8665; and
references cited therein. (b) Olivero, S.; Perriot, R.; Dunach,
E.; Baru, A. R.; Bell, E. D.; Mohan, R. S. Synlett 2006, 2013.
(11) (a) Cui, Y.-M.; Huang, Q.-Q.; Xu, J.; Chen, L.-L.; Li, J.-Y.;
Ye, Q.-Z.; Li, J.; Nan, F.-J. Bioorg. Med. Chem. Lett. 2005,
15, 4130. (b) Jung, Y. H.; Kim, J. D. Arch. Pharm. Res.
2005, 4, 382.
Acknowledgment
This work was supported by Ministero dell’Università e della
Ricerca and by the University of Torino.
(12) Bernardon, J.-M. WO 9733856, 1997; Chem. Abstr. 1997,
127, 292999.
(13) De S, K.; Gibbs, R. A. Tetrahedron Lett. 2005, 46, 8345; and
references cited therein.
References
(1) (a) Barbero, M.; Cadamuro, S.; Dughera, S.; Venturello, P.
Synlett 2007, 2209. (b) Barbero, M.; Cadamuro, S.;
Dughera, S.; Venturello, P. Synthesis 2008, 1379.
(2) Barbero, M.; Cadamuro, S.; Dughera, S.; Venturello, P.
Synthesis 2008, 3625.
(3) Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S. Eur. J.
Org. Chem. 2009, 430.
(4) Barbero, M.; Cadamuro, S.; Deagostino, A.; Dughera, S.;
Larini, P.; Occhiato, G.; Prandi, C.; Tabasso, S.; Venturello,
P.; Vulcano, R. Synthesis 2009, 2260.
(14) (a) Wilkinson, J. A.; Rossington, S. B.; Leonard, J.; Hussain,
N. Tetrahedron Lett. 2004, 45, 1191. (b) Wilkinson, J. A.;
Rossington, S. B.; Coe, N. A.; Hirst, N.; McGown, A. T.;
Leonard, J.; Hussain, N. Lett. Drug Des. Discovery 2007, 4,
246. (c) Wilkinson, J. A.; Foretia, D.; Rossington, S. B.;
Heagerty, A.; Leonard, J.; Hussain, N.; Austin, C. Eur. J.
Pharmacol. 2007, 561, 160. (d) Zhao, X.-L.; Chen, Y.-J.;
Liu, L.; Wang, D. Chin. J. Chem. 2007, 25, 1312.
(15) Barbero, M.; Crisma, M.; Degani, I.; Fochi, R.; Perracino, P.
Synthesis 1998, 1171.
(5) Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S.; Ghigo,
(16) Meskens, F. A. J. Synthesis 1981, 501.
(17) Csákÿ, A. G.; Máximo, M.; Plumet, J.; Rámila, A.
G. Eur. J. Org. Chem. 2009, 4346.
(6) (a) Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 16,
1295. (b) Sakurai, H. Pure Appl. Chem. 1982, 54, 1.
(c) Sakurai, H.; Sasaki, K.; Hayashi, J.; Hosomi, A. J. Org.
Chem. 1984, 49, 2808. (d) Sakurai, H. Pure Appl. Chem.
1985, 57, 1759. (e) Hosomi, A. Acc. Chem. Res. 1988, 21,
200.
(7) For some recent significant examples of the Hosomi–
Sakurai reaction, see: (a) Reddy, U. C.; Bondalapati, S.;
Saikia, K. A. Eur. J. Org. Chem. 2009, 1625. (b) Sabot, C.;
Guerard, K. C.; Canesi, S. Chem. Commun. 2009, 2941.
(c) Kumar, R. S. C.; Reddy, G. V.; Babu, K. S.; Rao, J. M.
Chem. Lett. 2009, 38, 564. (d) Sabot, C.; Commare, B.;
Duceppe, M.-A.; Nahi, S.; Guerard, K. C.; Canesi, S. Synlett
2008, 3226. (e) Spangenberg, T.; Airiau, E.; Thuong, M. B.
T.; Donnard, M.; Billet, M.; Mann, A. Synlett 2008, 2859.
(f) Xu, L.-W.; Yang, M.-S.; Qiu, H.-Y.; Lai, G.-Q.; Jiang,
Tetrahedron Lett. 1999, 40, 6485.
(18) Torii, S.; Inokuchi, T.; Takagishi, S.; Horike, H.; Kuroda,
H.; Uneyama, K. Bull. Chem. Soc. Jpn. 1987, 60, 2173.
(19) Maeda, H.; Shono, K.; Ohmori, H. Chem. Pharm. Bull.
1994, 42, 1808.
(20) Jung, M. E.; Maderna, A. J. Org. Chem. 2004, 69, 7755.
(21) Mahrwald, R.; Quint, S. Tetrahedron 2000, 56, 7463.
(22) Yoshizawa, K.; Shioiri, T. Tetrahedron 2007, 63, 6259.
(23) Podder, S.; Choudhury, J.; Roy, S. J. Org. Chem. 2007, 72,
3129.
(24) Okajima, M.; Soga, K.; Nokami, T.; Suga, S.; Yoshida, J.
Org. Lett. 2006, 5005.
(25) Mayr, H.; Bug, T.; Gotta, M. F.; Hering, N.; Irrgang, B.;
Janker, B.; Kempf, B.; Loos, R.; Ofial, A. R.; Remennikov,
G.; Schimmel, H. J. Am. Chem. Soc. 2001, 123, 9500.
Synthesis 2010, No. 2, 315–319 © Thieme Stuttgart · New York