Synthesis of substituted 2-vinylfurans

Article abstract of DOI:10.1016/j.tet.2015.10.072

K₂CO₃ (3a)-mediated (3+2) cycloisomerization of β-ketosulfones 1 with 1,4-dichloro-2-butyne (2) in acetone afforded substituted 2-vinylfurans 4 at 56 °C for 8 h in good yields. The one-pot tandem route provides mild, facile and efficient reaction conditions. A plausible mechanism has been discussed and proposed.

Full text of DOI:10.1016/j.tet.2015.10.072

Accepted Manuscript
Synthesis of Substituted 2-Vinylfurans
Chieh-Kai Chan, Yi-Ju Lu, Meng-Yang Chang
PII:
S0040-4020(15)30172-1
10.1016/j.tet.2015.10.072
TET 27244
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 25 September 2015
Revised Date: 21 October 2015
Accepted Date: 26 October 2015
Please cite this article as: Chan C-K, Lu Y-J, Chang M-Y, Synthesis of Substituted 2-Vinylfurans,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.10.072.
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Synthesis of Substituted 2-Vinylfurans
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Chieh-Kai Chan, Yi-Ju Lu and Meng-Yang Chang*
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
R
O
O
R
O
O
Cl
S
K
2 3
CO , acetone
S
+
Cl
Ar
Ar
O 2
O

ACCEPTED MANUSCRIPT
Tetrahedron
1
TETRAHEDRON
Pergamon
Synthesis of Substituted 2-Vinylfurans
Chieh-Kai Chan, Yi-Ju Lu and Meng-Yang Chang*
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
Abstract—K CO (3a)-mediated (3+2) cycloisomerization of β-ketosulfones 1 with 1,4-dichloro-2-butyne (2) in acetone
2
3
o
afforded substituted 2-vinylfurans 4 at 56 C for 8 h in good yields. The one-pot tandem route provides mild, facile and
efficient reaction conditions. A plausible mechanism has been discussed and proposed.
In continuation of our investigation on the applications
1
.
Introduction
of β-ketosulfones 1 (e.g. 2-arylpyrroles, vinylcyclopropanes,
,6-diaryltetrahydropyrans, 2-arylfurans, pyridazines and
2
8,9
Polysubstituted furans represent an important class of
tetralins), a facile one-pot K CO (3a)-mediated synthesis
2 3
five-membered oxygenated heterocycles in many natural
products and drug molecules. Numerous furan derivatives
have been shown to exhibit a wide range of potential
biological activities. Accordingly, the development of new
and efficient synthetic approaches to multi-functionalized
furans has attracted tremendous attention. To the best of
our knowledge, few direct utilizations of transition metal-
free base or phosphine -induced one-pot tandem atom-
of 2-vinylfurans 4 with diversified aryl and sulfonyl groups
is developed, including (1) an intermolecular α-
propargylation of β-ketosulfones 1 with 1,4-dichloro-but-2-
yne (2) and (2) an intramolecular in-situ cycloisomerization
of the resulting enolate of γ-alkynone. After further
comparing literature reports on the preparation of 2-
vinylfurans, our study found that no reports have been
documented on the synthesis of 4-sulfonyl 2-vinylfurans
1
2
3
4
-5
6
7
10
economical cycloisomerization to construct a furan ring
(
4). Herein, we describe a one-pot route of 4 via a K CO -
2 3
have been reported. As shown in Scheme 1, Reddy et al.
reported the DBU-mediated [3+2] annulation of enynes and
mediated (3+2) cycloisomerization of 1 with 2. 2-
Vinylfuran is a versatile building block in the synthesis of
natural products (eg rubifolide, acersolide) and a useful
1
,3-dicarbonyl compounds via Michael addition/5-exo-dig-
4a
6,11-12
cycloisomerization. Eberbach et al. reported on NaH-
synthetic intermediate.
5
n
promoted intramolecular cyclization of pentyone. PBu -
3
initiated the preparation of 2-vinylfurans via a tandem 1,6-
addition of phosphine toward the enynes, ring closure,
followed by Wittig olefination which was developed by
Kuroda et al.. However, new metal-free synthetic routes
for furans from alkynes still represent continuing needs in
the organic field.
2. Results and discussion
Initially, treatment of the mode substrate 1a (R = Tol, Ar
= Ph), prepared from nucleophilic substitution of 2-bromo-
1-phenylethanone with toluenesulfinic acid sodium salt
6
(TolSO Na) in a co-solvent of dioxane and water (v/v = 1/1)
2
with K CO (3a, 3.0 equiv) and 1,4-dichloro-but-2-yne (2,
2
3
o
Scheme 1. Base mediated route of substituted furans
1.1 equiv) in acetone (10 mL) at 25 C produced 4a (68%)
along with a 31% yield of 1a, as shown in Table 1 and
entry 1. In entries 2-5, NaH (3b), Cs CO (3c), DBU (3d)
Reddy, Michael addition / cycloisomerization
Eberbach, cycloisomerization
2
3
O
O
O
O
O
DBU4a Ph
Ph
NaH5
and t-BuOK (3e) were also examined for the generation of
Ph
Ph
Ph
+
Ph Ph
o
4
a at 25 C for 8 h. For generating 4a, 3a provided a better
yield (68%) than 3b (32%), 3c (42%), 3d (25%) and 3e
36%). On the basis of a higher yield and activity, low
Ph
CO Me
O
O
O
2
CO Me
Ph
Ph
2
(
Kuroda, cycloisomerization / Wittig olefination Our work, cycloisomerization
O
toxicity and relatively low price, 3a was chosen as the
appropriate base for synthetizing 4a. Then, the use of other
solvents (10 mL) was examined (entries 6-8). In
R
O
Cl
R
O
S
PBun
6a-b
S
1
2 3
K CO (3a) O
3
Ph
O
2
PhCHO
Ph
+
Ph
O
Ph
Ar
O
Ar
Ph
O
Cl
2
4
comparison with these solvents (DMF, MeCN and MeNO2),
acetone was a better solvent for the formation of 4a.
—
——
Keywords: Vinylfurans; Cycloisomerization; β-Ketosulfones.
Furthermore, controlling K CO3 (3a)/acetone as the
2
*Corresponding author. Tel.: +886 7 3121101 ext 2220
combination, equivalent of base, reaction concentration,
temperature and time were studied. When using 5 or 10
e-mail: mychang@kmu.edu.tw

ACCEPTED MANUSCRIPT
2
Tetrahedron
equivalents of 3a, the provided yield of 4a was similar to 3
equivalents (entries 9-10). By adjusting the reaction
concentration (10 ‰ 20 mL), similar results (60%) were
observed (entry 11). When increasing the reaction
temperature from 25 C to reflux (56 C), 78% of 4a was
yielded (entry 12). When elongating the reaction time (8 ‰
The possible reaction mechanism (see Scheme 2) should
be initiated to form intermediate A by deprotonation of 1a
with K CO . After intermolecular α-propargylation of A
with 2, B could be generated. Deprotonation of B should
give enolates C1 and C2 with the equilibrium of the E/Z-
2
3
o
o
isomer mixture. Then, intramolecular S 2’ propargylation
N
2
0 h), a poorer yield (72%) was observed (entry 13). Based
of C2 leads to an alternative D with a cyclic allene motif,
which, following cycloisomerisation of D, is able to
provide 4a.
on the above results, we envisioned that K CO3 (3
equiv)/acetone (10 mL)/reflux/8 h should constitute optimal
2
conditions for forming 4a via a one-pot reaction of 1a with
a
2
.
Table 2. Synthesis of 4
a
R
O
O
Cl
R
O
Table 1. One-pot conditions
S
K
2
CO
3
S
O
+
Cl acetone
Ar
Tol
O
Cl
O
O
Ar
O
4
Tol
S
base, solvent
conditions
S
1
2
O
+
O
Cl
Ph
b
O
Ph
O
entry 1, Ar =, R =,
4, yield%
4a, 78
4b, 76
4c, 80
4d, 76
4e, 83
4f, 82
4g, 75
4h, 76
4i, 72
1a
2
4a
1
2
3
4
5
6
7
8
9
1a, Ph, 4-MeC H4
6
o
b-c
entry 3 (equiv), solvent (mL), temp ( C), time (h) yield (%)
1b, 4-FC H , 4-MeC H
4
6
4
6
1
2
3
4
5
6
7
8
9
K CO 3a (3), acetone (10), 25, 8
68
32
42
25
36
48
50
52
62
58
60
78
72
2
3
1c, 4-MeOC H , 4-MeC H
4
6
4
6
NaH 3b (3), THF (10), 25, 8
1d, 4-MeC H , 4-MeC H
4
6
4
6
Cs CO 3c (3), acetone (10), 25, 8
2
3
1e, 4-CF C H , 4-MeC H
4
3
6
4
6
DBU 3d (3), THF (10), 25, 8
t-BuOK 3e (3), acetone (10), 25, 8
K CO 3a (3), DMF (10), 25, 8
1f, 4-PhC H , 4-MeC H
4
6
4
6
1g, 2-naphthalene, 4-MeC H4
6
2
3
1h, 4-FC H , Ph
6
4
K CO 3a (3), MeCN (10), 25, 8
2
3
1i, 4-MeOC H , Ph
6
4
K CO 3a (3), MeNO (10), 25, 8
2
3
2
1
0
1
2
3
4
5
6
1j, 4-PhC H , Ph
4j, 80
4k, 73
4l, 74
6
4
K CO 3a (5), acetone (10), 25, 8
2
3
1
1
1
1
1
1
1k, 4-MeC H , Me
6 4
1
0
1
2
3
K CO 3a (10), acetone (10), 25, 8
2 3
1l, 4-PhC H , Me
6
4
1
1
1
K CO 3a (3), acetone (20), 25, 8
2 3
1m, Ph, 3-MeC H4
4m, 81
4n, 76
4o, 72
4p, 75
6
K CO 3a (3), acetone (10), 56, 8
2
3
1n, Ph,4-t-BuC H4
6
K CO 3a (5), acetone (10), 56, 20
Reactions were run on a 0.5 mmol scale with 1a.
2
3
1o, Ph, 4-MeOC H4
6
a
b
c
6
1p, Ph, 4-FC H4
Isolated yields.
a
The 2-vinylfuran synthesis was run on a 0.5 mmol scale
with 1, K CO (3a) (3.0 equiv), acetone (10 mL), 8 h, 56 C.
Isolated yield.
1
a was recovered (entry 1, 31%; entry 2, 45%; entry 3,
3%; entry 4, 60%; entry 5, 43%; entry 6, 24%; entries 7-8,
0%; entry 9, 16%; entry 10, 15%; entry 11, 10%; entries
2-13, ~5%).
o
2
3
3
2
1
b
With optimized conditions in hand (Table 1, entry 12),
we further explored the substrate scope of the one-pot
reaction, and the results were shown in Table 2. For
adjusting Ar and R substituents of β-ketosulfones 1a-p (Ar
Scheme 2. Possible mechanism
deprotonation /
intermolecular α-propargylation
deprotonation
Tol
=
Ph, 4-FC H , 4-MeOC H , 4-MeC H , 4-CF C H , 4-
6 4 6 4 6 4 3 6 4
Tol
O
Cl
2
Cl Tol
O
O
PhC
6
H
4
, 2-naphthalene; R = 4-MeC
H , Ph, Me, 3-MeC H ,
6 4 6 4
K
2
CO
3
S
A
S
H
K
2
CO
3
S
1a
O
O
O
O
4-t-BuC
6
H
4
, 4-MeOC , 4-FC ), 4a-p were provided in
6
H
4
H
6 4
Ph
Ph
72-83% yields (entries 1-16). For the Ar and R groups of
1a-p, the phenyl ring, with both electron-withdrawing and
electron-donating substituents, were well tolerated,
providing the desired skeleton of 2-vinylfuran in good
yields. The structure of 4h was determined by single-
O
O
Ph
Cl
Cl
B
C1
cycloisomerization
intramolecular
N
2' propargylation
S
13
Tol
O
Tol
O
Tol
O
crystal X-ray crystallography (Figure 1).
S
S
H
S
2 3
K CO
O
O
O
Ph
O
Ph
O
D
C
Ph
O
Cl
4a
C2

ACCEPTED MANUSCRIPT
Tetrahedron
3
Figure 1. X-ray structure of 4h
Figure 2. X-ray structure of 7
3
.
Conclusion
In summary, we have developed a mild, facile and one-
pot synthesis of substituted 2-vinylfurans 4 in good yields
via a K CO -mediated (3+2) cycloisomerization of β-
2
3
ketosulfones 1 with 1,4-dichloro-but-2-yne (2) under an
intermolecular and intramolecular propargylation process.
A plausible mechanism has been proposed. The structure of
the key 4h is confirmed by X-ray crystallography. Further
investigation regarding synthetic applications of β-
ketosulfones will be conducted and published in due course.
Scheme 3. Reactions of 5a-f with 2
O
O
Cl
Y
2 3
K CO
Y
+
Cl acetone
4. Experimental section
Ar
O
Ar
O
Y = OEt
2
Y = OEt
6a, Ar = Ph (68%)
6b, Ar = 4-MeOC
6c, Ar = 4-NO
Y = NH
6d, Ar = Ph (trace)
Y = Ph
6e, Ar = Ph (trace)
Y = Me
4
.1. General. All other reagents and solvents were obtained
5a, Ar = Ph
5b, Ar = 4-MeOC
5c, Ar = 4-NO
H
4
(52%)
2 6 4
C H (60%)
6
H
4
6
from commercial sources and used without further
purification. Reactions were routinely carried out under an
atmosphere of dry nitrogen with magnetic stirring. Products
in organic solvents were dried with anhydrous magnesium
sulfate before concentration in vacuo. Melting points were
2
C
6
H
4
Y = NH
d, Ar = Ph
Y = Ph
e, Ar = Ph
Y = Me
f, Ar = Ph
2
2
5
5
5
6f, Ar = Ph (trace)
1
13
determined with a SMP3 melting apparatus. H and C NMR
spectra were recorded on a Varian INOVA-400 spectrometer
operating at 400 and at 100 MHz, respectively. Chemical
shifts (δ) are reported in parts per million (ppm) and the
coupling constants (J) are given in Hertz. High resolution
mass spectra (HRMS) were measured with a mass
spectrometer Finnigan/Thermo Quest MAT 95XL. X-ray
crystal structures were obtained with an Enraf-Nonius FR-
590 diffractometer (CAD4, Kappa CCD).
Changing the α-substituent from the sulfonyl group to
the ethyl ester groups (Y = OEt; 5a, Ar = Ph; 5b, Ar = 4-
MeOC H ; 5c, Ar = 4-NO C H ), 6a-c were isolated in
6
4
2
6
4
5
2%-68% yields via one-pot cycloisomerization of β-
ketoesters 5a-c, as shown in Scheme 3. Based on the results,
lower yields of 6a-c were observed. However, attempts to
react β-ketoamide 5d (Y = NH ; Ar = Ph) with 2 failed to
2
afford 6d under one-pot conditions. Similarly, trace
amounts of β-diketones 6e (Y = Ar = Ph) and 6f (Y = Me,
Ar = Ph) were yielded, respectively. Compared with the
given yields of 1,3-dicarbonyl synthons, β-ketosulfone 1
provided better yields for generating the 2-vinylfuran
skeleton.
4
.2. A representative synthetic procedure of compounds 4a-p
is as follows: K CO (3a, 210 mg, 1.5 mmol) was added to a
2
3
solution of β-ketosulfones 1a-p (0.5 mmol) in acetone (10
o
o
mL) at 25 C. The reaction mixture was stirred at 25 C for
0 min. 1,4-dichloro-2-butyne (2, 68 mg, 0.55 mmol) was
1
o
added to the reaction mixture at 25 C. The reaction mixture
was stirred at 56 C for 8 h. The reaction mixture was cooled
to 25 C and the solvent was concentrated. The residue was
Scheme 4. Synthesis of 7
o
o
O
Me
O
Me
OH
Me
Ph
K
2
CO
3
diluted with water (10 mL) and the mixture was extracted
with CH Cl (3 x 20 mL). The combined organic layers were
acetone
2
2
Ph
Ph
O
OH
7 (64%)
O
washed with brine, dried, filtered and evaporated to afford
crude product. Purification on silica gel (hexanes/EtOAc =
5
f
7a (no detected)
1
5/1~8/1) afforded 4a-p.
By the removal of 2, 5f was converted into a sole β-
hydroxy (Z)-enone 7 with a full-conjugation in a 64% yield
in the presence of K CO , as shown in Scheme 4. Under
4
.2.1. 2-Phenyl-3-(toluene-4-sulfonyl)-5-vinylfuran (4a).
o
Yield = 78% (126 mg); Colorless solid; mp = 62-63 C
2
3
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
above conditions, no formation of 7a was observed. The
structural framework of 7 was determined by single-crystal
1
calcd for C H O S 325.0899, found 325.0903; H NMR
19 17
3
1
3
(
400 MHz, CDCl ): δ 7.91-7.89 (m, 2H), 7.68 (d, J = 8.4 Hz,
X-ray crystallography (Figure 2).
3

ACCEPTED MANUSCRIPT
4
Tetrahedron
1
2
6
1
H), 7.44-7.41 (m, 3H), 7.19 (d, J = 8.4 Hz, 2H), 6.67 (s, 1H), calcd for C H O S 401.1212, found 401.1213; H NMR
25
21
3
.46 (dd, J = 11.2, 17.6 Hz, 1H), 5.78 (dt, J = 0.4, 17.6 Hz,
(400 MHz, CDCl ): δ 8.02-7.99 (m, 2H), 7.75-7.72 (m, 2H),
7.69-7.64 (m, 4H), 7.50-7.46 (m, 2H), 7.41-7.37 (m, 1H),
3
13
H), 5.31 (dd, J = 0.4, 11.2 Hz, 1H), 2.35 (s, 3H); C NMR
(
100 MHz, CDCl ): δ 153.79, 151.55, 144.17, 138.86, 129.99, 7.22 (d, J = 8.0 Hz, 2H), 6.69 (s, 1H), 6.48 (dd, J = 11.6, 17.6
3
1
1
28.57 (2x), 128.65 (2x), 128.27 (2x), 128.21, 127.06 (2x),
25.54, 123.67, 115.34, 109.96, 21.50.
Hz, 1H), 5.81 (d, J = 17.6 Hz, 1H), 5.33 (d, J = 11.6 Hz, 1H),
13
2.36 (s, 3H); C NMR (100 MHz, CDCl ): δ 153.51, 151.60,
3
1
44.24, 142.56, 140.06, 138.94, 129.65 (2x), 128.99 (2x),
4
.2.2. 2-(4-Fluorophenyl)-3-(toluene-4-sulfonyl)-5-vinylfuran
o
128.90 (2x), 127.88, 127.11 (3x), 127.07 (2x), 126.92 (2x),
125.53, 123.71, 115.40, 110.19, 21.53.
(4b). Yield = 76% (130 mg); Colorless solid; mp = 61-62 C
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
1
calcd for C H FO S 343.0804, found 343.0812; H NMR
4.2.7. 2-Naphthalen-2-yl-3-(toluene-4-sulfonyl)-5-vinylfuran
(4g). Yield = 75% (140 mg); Colorless solid; mp = 58-59 C
H), 7.22 (d, J = 8.0 Hz, 2H), 7.15-7.09 (m, 2H), 6.65 (s, 1H), (recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
1
9
16
3
o
(
400 MHz, CDCl ): δ 7.93-7.88 (m, 2H), 7.67 (d, J = 8.4 Hz,
3
+
2
6
5
1
.45 (dd, J = 11.2, 17.6 Hz, 1H), 5.77 (d, J = 17.6 Hz, 1H),
calcd for C H O S 375.1055, found 375.1056; H NMR
(400 MHz, CDCl ): δ 8.46 (d, J = 0.8 Hz, 1H), 7.97 (dd, J =
23 19 3
1
3
.32 (d, J = 12.0 Hz, 1H), 2.37 (s, 3H); C NMR (100 MHz,
3
CDCl ): δ 163.68 (d, J = 250.2 Hz), 152.80, 151.61, 144.33,
2.0, 8.8 Hz, 1H), 7.94-7.91 (m, 1H), 7.87 (d, J = 8.8 Hz, 1H),
7.86-7.84 (m, 1H), 7.71 (d, J = 8.4 Hz, 2H), 7.57-7.52 (m,
2H), 7.16 (d, J = 8.0 Hz, 2H), 6.75 (s, 1H), 6.51 (dd, J = 11.2,
17.2 Hz, 1H), 5.84 (d, J = 17.2 Hz, 1H), 5.35 (d, J = 11.2 Hz,
3
1
1
38.79, 130.85 (d, J = 9.1 Hz, 2x), 129.66 (2x), 127.05 (2x),
25.47, 124.50 (d, J = 3.8 Hz), 123.63, 115.51 (d, J = 22.0
Hz, 2x), 115.46, 109.88, 21.53.
13
1
1
H), 2.32 (s, 3H); C NMR (100 MHz, CDCl ): δ 153.76,
51.72, 144.21, 138.89, 133.70, 132.72, 129.60 (2x), 128.99,
3
4
.2.3. 2-(4-Methoxyphenyl)-3-(toluene-4-sulfonyl)-5-
vinylfuran (4c). Yield = 80% (142 mg); Colorless gum;
+
128.89, 127.99, 127.68, 127.37, 127.14 (2x), 126.64, 125.86,
125.58, 125.13, 123.76, 115.46, 110.29, 29.68.
HRMS (ESI, M +1) calcd for C H O S 355.1004, found
2
0
19
4
1
3
2
55.1011; H NMR (400 MHz, CDCl ): δ 7.87 (d, J = 8.8 Hz,
H), 7.68 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.94
3
4.2.8.
3-Benzenesulfonyl-2-(4-fluorophenyl)-5-vinylfuran
o
(
d, J = 9.2 Hz, 2H), 6.64 (s, 1H), 6.44 (dd, J = 11.2, 17.6 Hz,
(4h). Yield = 76% (125 mg); Colorless solid; mp = 65-67 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
calcd for C H FO S 329.0648, found 329.0645; H NMR
+
1
3
1
H), 5.75 (d, J = 17.6 Hz, 1H), 5.28 (d, J = 11.6 Hz, 1H),
1
3
1
.86 (s, 3H), 2.36 (s, 3H); C NMR (100 MHz, CDCl ): δ
3
18 14
3
60.99, 154.12, 151.00, 144.05, 139.11, 130.28 (2x), 129.59
(400 MHz, CDCl ): δ 7.92-7.87 (m, 2H), 7.78 (d, J = 8.4 Hz,
3
(
(
2x), 126.99 (2x), 123.76, 120.90, 114.83, 114.30, 113.77
2x), 110.01, 55.35, 29.68.
2H), 7.55-7.51 (m, 1H), 7.44-7.40 (m, 2H), 7.15-7.09 (m,
2H), 6.67 (s, 1H), 6.46 (dd, J = 11.6, 17.6 Hz, 1H), 5.78 (d, J
13
=
17.6 Hz, 1H), 5.33 (d, J = 11.6 Hz, 1H); C NMR (100
4
.2.4. 3-(Toluene-4-sulfonyl)-2-p-tolyl-5-vinylfuran (4d).
o
MHz, CDCl ): δ 163.71 (d, J = 250.2 Hz), 153.07, 151.71,
3
Yield = 76% (128 mg); Colorless solid; mp = 66-67 C
(
calcd for C H O S 339.1055, found 339.1053; H NMR
(
8
2
=
+
141.62, 133.32, 130.88 (d, J = 8.4 Hz, 2x), 129.03 (2x),
126.97 (2x), 125.10, 124.39 (d, J = 3.0 Hz), 123.57, 115.62
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
1
2
0
19
3
(
d, J = 3.7 Hz, 2x), 115.42, 109.82. Single-crystal X-Ray
400 MHz, CDCl ): δ 7.80 (d, J = 8.4 Hz, 2H), 7.69 (d, J =
3
diagram: crystal of compound 4h was grown by slow
diffusion of EtOAc into a solution of compound 4h in
CH Cl to yield colorless prisms. The compound crystallizes
.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.4 Hz,
H), 6.65 (s, 1H), 6.45 (dd, J = 11.2, 17.6 Hz, 1H), 5.76 (d, J
2
2
17.2 Hz, 1H), 5.30 (d, J = 11.2 Hz, 1H), 2.40 (s, 3H), 2.36
1
3
in the orthorhombic crystal system, space group P 21/n, a =
(
s, 3H); C NMR (100 MHz, CDCl ): δ 154.18, 151.27,
3
8
1
2
.2554(4) Å, b = 16.7563(10) Å, c = 11.6782(7) Å, V =
1
1
2
44.08, 140.33, 139.05, 129.59 (2x), 129.03 (2x), 128.56 (2x),
27.05 (2x), 125.48, 124.85, 123.74, 115.08, 109.99, 21.53,
1.47.
3
3
541.56(15) Å , Z = 4, d
= 1.415 mg/cm , F(000) = 680,
calcd
o
θ range 2.683~26.401 , R indices (all data) R1 = 0.0532,
wR2 = 0.1334.
4
.2.5. 3-(Toluene-4-sulfonyl)-2-(4-trifluoromethylphenyl)-5-
4
.2.9. 3-Benzenesulfonyl-2-(4-methoxyphenyl)-5-vinylfuran
vinylfuran (4e). Yield = 83% (163 mg); Colorless solid; mp =
7
(
3
2
o
o
(4i). Yield = 72% (122 mg); Colorless solid; mp = 56-57 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
calcd for C19
5-76 C (recrystallized from hexanes and EtOAc); HRMS
+
+
ESI, M +1) calcd for C H F O S 393.0772, found
2
0
16
3
3
1
1
H
17
O
4
S 341.0848, found 341.0852; H NMR
93.0776; H NMR (400 MHz, CDCl ): δ 8.06 (d, J = 8.4 Hz,
3
(
400 MHz, CDCl ): δ 7.86 (d, J = 9.2 Hz, 2H), 7.79 (d, J =
3
H), 7.70 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 7.24
d, J = 8.4 Hz, 2H), 6.67 (s, 1H), 6.48 (dd, J = 11.6, 17.6 Hz,
9
=
.2 Hz, 2H), 7.53-7.49 (m, 1H), 7.43-7.39 (m, 2H), 6.94 (d, J
8.8 Hz, 2H), 6.66 (s, 1H), 6.45 (dd, J = 11.2, 17.6 Hz, 1H),
5.75 (d, J = 17.6 Hz, 1H), 5.29 (d, J = 11.2 Hz, 1H), 3.86 (s,
(
1
2
1
1
1
H), 5.82 (d, J = 17.6 Hz, 1H), 5.37 (d, J = 11.6 Hz, 1H),
13
.38 (s, 3H); C NMR (100 MHz, CDCl ): δ 152.38, 151.58,
3
13
3
1
1
H); C NMR (100 MHz, CDCl ): δ 161.05, 154.41, 151.10,
3
44.62, 138.48, 131.59, 131.44, 129.77 (2x), 128.84 (4x),
27.16, 127.12 (2x), 125.26 (q, J = 3.8 Hz), 123.48, 116.24,
10.13, 21.53.
41.95, 133.12, 130.31 (3x), 128.95 (2x), 126.92 (2x), 123.71,
20.78, 114.96, 113.79 (2x), 109.96, 55.35.
4
.2.10. 3-Benzenesulfonyl-2-biphenyl-4-yl-5-vinylfuran (4j).
4
.2.6.
2-Biphenyl-4-yl-3-(toluene-4-sulfonyl)-5-vinylfuran
o
o
Yield = 80% (154 mg); Colorless solid; mp = 72-73 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
(4f). Yield = 82% (164 mg); Colorless solid; mp = 95-96 C
+
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)

ACCEPTED MANUSCRIPT
Tetrahedron
5
1
calcd for C H O S 387.1055, found 387.1056; H NMR
(dd, J = 11.2, 17.6 Hz, 1H), 5.78 (dd, J = 0.4, 17.6 Hz, 1H),
5.31 (dd, J = 0.4, 11.2 Hz, 1H), 3.80 (s, 3H); C NMR (100
2
4
19
3
13
(
400 MHz, CDCl ): δ 8.01-7.98 (m, 2H), 7.86-7.84 (m, 2H),
3
7
.69-7.63 (m, 4H), 7.55-7.37 (m, 6H), 6.71 (s, 1H), 6.49 (dd,
MHz, CDCl ): δ 163.33, 153.51, 151.47, 133.34, 130.85,
3
J = 11.6, 17.2 Hz, 1H), 5.82 (d, J = 17.2 Hz, 1H), 5.34 (d, J =
129.94, 129.28 (2x), 128.63 (2x), 128.26 (2x), 125.96, 123.69,
1
3
1
1
1
1
1.6 Hz, 1H); C NMR (100 MHz, CDCl ): δ 153.81, 151.71, 115.29, 114.11 (2x), 109.89, 55.56.
44.67, 141.81, 140.02, 133.25, 129.02 (4x), 128.91 (2x),
27.91 (2x), 127.08 (2x), 127.04 (2x), 126.94 (2x), 125.17,
23.67, 115.53, 110.14.
3
4
.2.16. 3-(4-Fluorobenzenesulfonyl)-2-phenyl-5-vinylfuran
o
(4p). Yield = 75% (123 mg); Colorless solid; mp = 70-71 C
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1)
1
4
=
.2.11. 3-Methanesulfonyl-2-p-tolyl-5-vinylfuran (4k). Yield
calcd for C H FO S 329.0648, found 329.0651; H NMR
18
14
3
o
73% (96 mg); Colorless solid; mp = 70-71
C
(400 MHz, CDCl ): δ 7.88-7.85 (m, 2H), 7.80-7.76 (m, 2H),
3
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1) 7.45-7.41 (m, 3H), 7.08-7.04 (m, 2H), 6.70 (s, 1H), 6.47 (dd,
1
calcd for C H O S 263.0742, found 263.0745; H NMR
J = 11.2, 17.6 Hz, 1H), 5.80 (dd, J = 0.4, 17.6 Hz, 1H), 5.33
1
4
15
3
13
(
400 MHz, CDCl ): δ 7.90 (d, J = 8.0 Hz, 2H), 7.29 (d, J =
(dd, J = 0.4, 11.2 Hz, 1H); C NMR (100 MHz, CDCl ): δ
3
3
8
5
1
.4 Hz, 2H), 6.71 (s, 1H), 6.50 (dd, J = 11.6, 17.6 Hz, 1H),
.83 (dd, J = 0.4, 17.6 Hz, 1H), 5.35 (dd, J = 0.4, 11.2 Hz,
165.37 (d, J = 254.0 Hz), 154.12, 151.75, 137.72 (d, J = 3.0
Hz), 130.22, 129.84 (d, J = 9.1 Hz, 2x), 128.70 (2x), 128.35
(2x), 128.01, 125.17, 123.57, 116.21 (d, J = 22.8 Hz, 2x),
115.66, 109.69.
1
3
H), 3.00 (s, 3H), 2.42 (s, 3H); C NMR (100 MHz, CDCl ):
3
δ 151.72, 151.38, 140.67, 129.53 (2x), 128.15 (2x), 125.41,
1
24.05, 123.69, 115.38, 109.68, 43.71, 21.47.
4
.3. A representative synthetic procedure of 6a-c is as follows:
4
.2.12. 2-Biphenyl-4-yl-3-methanesulfonyl-5-vinylfuran (4l).
K CO (3a, 210 mg, 1.5 mmol) was added to a solution of β-
ketoesters 5a-c (0.5 mmol) in acetone (10 mL) at 25 C. The
o
2
3
o
o
Yield = 74% (120 mg); Colorless solid; mp = 113-114 C
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1) reaction mixture was stirred at 25 C for 10 min. 1,4-
1
calcd for C H O S 325.0899, found 325.0903; H NMR
dichloro-2-butyne (2, 68 mg, 0.55 mmol) was added to the
1
9
17
3
(
400 MHz, CDCl ): δ 8.11 (d, J = 8.8 Hz, 2H), 7.72 (d, J =
reaction mixture at reflux. The reaction mixture was stirred at
3
o
o
8
7
1
3
1
1
.8 Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.50-7.46 (m, 2H),
.42-7.38 (m, 1H), 6.76 (s, 1H), 6.53 (dd, J = 11.2, 17.6 Hz,
H), 5.87 (d, J = 17.6 Hz, 1H), 5.39 (d, J = 11.2 Hz, 1H),
56 C for 8 h. The reaction mixture was cooled to 25 C and
the solvent was concentrated. The residue was diluted with
water (10 mL) and the mixture was extracted with CH Cl (3
2
2
13
.06 (s, 3H); C NMR (100 MHz, CDCl ): δ 153.11, 151.70,
x 20 mL). The combined organic layers were washed with
3
42.85, 139.86, 128.94 (2x), 128.57 (2x), 127.99, 127.40 (2x), brine, dried, filtered and evaporated to afford crude product.
27.07 (2x), 126.97, 124.65, 123.64, 115.69, 109.89, 43.85.
Purification on silica gel (hexanes/EtOAc = 20/1~10/1)
afforded 6a-c.
4
.2.13. 2-Phenyl-3-(toluene-3-sulfonyl)-5-vinylfuran (4m).
o
Yield = 81% (131 mg); Colorless solid; mp = 47-49 C
(
calcd for C H O S 325.0899, found 325.0902; H NMR
4.3.1. 2-Phenyl-5-vinyl-furan-3-carboxylic acid ethyl ester
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1) (6a). Yield = 68% (82 mg); Colorless oil; HRMS (ESI, M +1)
+
+
1
1
calcd for C H O 243.1021, found 243.1025; H NMR (400
1
9
17
3
15 15 3
(
400 MHz, CDCl ): δ 7.89-7.86 (m, 2H), 7.59-7.57 (m, 2H),
MHz, CDCl ): δ 8.03-8.00 (m, 2H), 7.46-7.40 (m, 3H), 6.70
3
3
7
.44-7.42 (m, 3H), 7.30-7.26 (m, 2H), 6.69 (s, 1H), 6.47 (dd,
J = 11.6, 17.6 Hz, 1H), 5.79 (d, J = 17.6 Hz, 1H), 5.32 (d, J =
(s, 1H), 6.51 (dd, J = 11.2, 17.6 Hz, 1H), 5.79 (dd, J = 1.2,
17.6 Hz, 1H), 5.28 (dd, J = 1.2, 11.2 Hz, 1H), 4.30 (q, J = 7.2
Hz, 2H), 1.33 (t, J = 7.2 Hz, 3H); C NMR (100 MHz,
13
13
1
1
1
1
1.6 Hz, 1H), 2.31 (s, 3H); C NMR (100 MHz, CDCl ): δ
3
54.03, 151.59, 141.50, 139.18, 134.00, 130.06, 128.79 (2x),
28.75 (2x), 128.21 (2x), 127.45, 125.40, 124.17, 123.70,
15.40, 109.95, 21.22.
CDCl ): δ 163.46, 156.50, 151.46, 129.68, 129.38, 128.42
3
(2x), 128.06 (2x), 124.24, 115.32, 114.02, 110.75, 60.55,
14.21.
4
.2.14. 3-(4-t-Butylbenzenesulfonyl)-2-phenyl-5-vinylfuran
4.3.2. 2-(4-Methoxyphenyl)-5-vinylfuran-3-carboxylic acid
o
(4n). Yield = 76% (139 mg); Colorless solid; mp = 61-62 C
ethyl ester (6b). Yield = 52% (71 mg); Colorless oil; HRMS
+
+
(
recrystallized from hexanes and EtOAc); HRMS (ESI, M +1) (ESI, M +1) calcd for C H O 273.1127, found 273.1129;
16
17
4
1
1
calcd for C H O S 367.1368, found 367.1377; H NMR
H NMR (400 MHz, CDCl ): δ 8.01 (d, J = 8.8 Hz, 2H), 6.96
2
2
23
3
3
(
2
400 MHz, CDCl ): δ 7.91-7.89 (m, 2H), 7.71 (d, J = 8.8 Hz,
H), 7.45-7.39 (m, 5H), 6.68 (s, 1H), 6.47 (dd, J = 11.2, 17.2
(d, J = 8.8 Hz, 2H), 6.67 (s, 1H), 6.49 (dd, J = 11.2, 17.6 Hz,
1H), 5.76 (dd, J = 0.8, 17.6 Hz, 1H), 5.25 (dd, J = 1.2, 11.2
3
Hz, 1H), 5.78 (d, J = 17.6 Hz, 1H), 5.31 (d, J = 11.2 Hz, 1H),
Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 3.86 (s, 3H), 1.34 (t, J =
13
13
1
1
.28 (s, 9H); C NMR (100 MHz, CDCl ): δ 157.11, 153.88,
51.58, 138.79, 129.99 (2x), 128.74 (2x), 128.27 (2x), 126.92
7.2 Hz, 3H); C NMR (100 MHz, CDCl ): δ 163.62, 160.51,
3
3
156.85, 150.83, 130.02 (2x), 124.29, 122.40, 114.05, 113.52
(3x), 110.75, 60.43, 55.33, 14.27.
(
2x), 125.99 (2x), 125.55, 123.73, 115.34, 110.01, 35.13,
3
0.98 (3x).
4
.3.3. 2-(4-Nitrophenyl)-5-vinylfuran-3-carboxylic acid ethyl
4
.2.15. 3-(4-Methoxybenzenesulfonyl)-2-phenyl-5-vinylfuran
ester (6c). Yield = 60% (86 mg); Colorless gum; HRMS (ESI,
M +1) calcd for C H NO 288.0872, found 288.0875; H
15 14 5
+
1
(4o). Yield = 72% (122 mg); Colorless gum; HRMS (ESI,
+
1
M +1) calcd for C H O S 341.0848, found 341.0851; H
NMR (400 MHz, CDCl ): δ 8.28 (br s, 4H), 6.76 (s, 1H),
19
17
4
3
NMR (400 MHz, CDCl ): δ 7.91-7.89 (m, 2H), 7.74-7.70 (m,
6.53 (dd, J = 11.2, 17.6 Hz, 1H), 5.86 (d, J = 17.6 Hz, 1H),
5.38 (d, J = 12.0 Hz, 1H), 4.33 (q, J = 7.2 Hz, 2H), 1.37 (t, J
3
2
H), 7.44-7.41 (m, 3H), 6.88-6.84 (m, 2H), 6.66 (s, 1H), 6.46

ACCEPTED MANUSCRIPT
6
Tetrahedron
1
3
B. Org. Lett. 2005, 7, 5409. (b) 7. (b) Hashmi, A. S. K.; Schwarz, L.;
Choi, J. H.; Frost, T. M. Angew. Chem. Int. Ed. 2000, 39, 2285. (c)
Zhou, C. Y.; Chan, P. W. H.; Che, C. M. Org. Lett. 2006, 8, 325. (d)
Dudnik, A. S.; Xia, Y.; Li, Y.; Gevorgyan, V. J. Am. Chem. Soc.
2010, 132, 7645. (e) Zhang, J.; Schmalz, H. G. Angew. Chem. Int. Ed.
=
1
1
7.2 Hz, 3H); C NMR (100 MHz, CDCl ): δ 162.96,
3
52.84, 135.32, 128.75 (2x), 123.89, 123.41 (4x), 118.20,
15.65, 111.32, 61.06, 14.19.
1
4
4
.4. 4-Hydroxy-4-phenylbut-3-en-2-one (7). K CO (3a, 420
2 3
mg, 3.0 mmol) was added to a solution of 5f (162 mg, 1.0
mmol) in acetone (10 mL) at 25 C. The reaction mixture was
stirred at 25 C for 10 min. The reaction mixture was stirred
at 56 C for 8 h. The reaction mixture was cooled to 25 C
and the solvent was concentrated. The residue was diluted
with water (10 mL) and the mixture was extracted with
CH Cl (3 x 20 mL). The combined organic layers were
washed with brine, dried, filtered and evaporated to afford
crude product. Purification on silica gel (hexanes/EtOAc =
2
006, 45, 6704. (f) Liu, X.; Pan, Z.; Shu, X.; Duan, X.; Liang, Y.
Synlett 2006, 1962. (g) Yao, T.; Zhang, X.; Larock, R. C. J. Org.
Chem. 2005, 70, 7679. (h) Yao, T.; Zhang, X.; Larock, R. C. J. Am.
Chem. Soc. 2004, 126, 11164. (i) Blanc, A.; Alix, A.; Weibel, J.-M.;
Pale, P. Eur. J. Org. Chem. 2010, 1644. (j) Blanc, A.; Tenbrink, K.;
Weibel, J.-M.; Pale, P. J. Org. Chem. 2009, 74, 5342. (k) Hashmi, A.
S. K.; Sinha, P. Adv. Synth. Catal. 2004, 346, 432. (l) Kirsch, S. F.
Org. Biomol. Chem. 2006, 4, 2076. (m) Jiang, H.; Yao, W.; Cao, H.;
Huang, H.; Cao, D. J. Org. Chem. 2010, 75, 5347. (n) Oh, C. H.;
Reddy, R.; Kim, A.; Rhim, C. Y. Tetrahedron Lett. 2006, 47, 5307.
o
o
o
o
2
2
(o) Arcadi, A.; Cerichelli, G.; Chiarini, M.; Giuseppe, S. D.;
Marinelli, F. Tetrahedron Lett. 2000, 41, 9195. (p) Arcadi, A.;
Cacchi, S.; Fabrizi, G.; Marinelli, F.; Parisi, L. M. Tetrahedron 2003,
2
0/1~10/1) afforded 7. Yield = 64% (104 mg); Colorless
solid; mp = 62-63 C (recrystallized from hexanes and
o
5
9, 4661. (q) Imagawa, H.; Kurisaki, T.; Nishizawa, M. Org. Lett.
+
2004, 6, 3679. (r) Hayes, S. J.; Knight, D. W.; Menzies, M. D.;
O’Halloran, M.; Tan, W.-F. Tetrahedron Lett. 2007, 48, 7709. (s)
Bai, H.-T.; Lin, H.-C.; Luh, T.-Y. J. Org. Chem. 2010, 75, 4591. (t)
Yi, C.; Blum, C.; Lehmann, M.; Keller, S.; Liu, S.-X.; Frei, G.;
Neels, A.; Hauser, J.; Schurch, S.; Decurtins, S. J. Org. Chem. 2010,
EtOAc); HRMS (ESI, M +1) calcd for C H O 431.1495,
2
6
23
6
1
found 431.1499; H NMR (400 MHz, CDCl ): δ 16.20 (br s,
3
1
(
1
H), 7.89-7.86 (m, 2H), 7.54-7.42 (m, 3H), 6.48 (s, 1H), 2.20
s, 3H); C NMR (100 MHz, CDCl ): δ 193.72, 183.29,
34.84, 132.22, 128.55 (2x), 126.95 (2x), 96.65, 25.77.
Single-crystal X-Ray diagram: crystal of compound 7 was
grown by slow diffusion of EtOAc into a solution of
compound 7 in CH Cl to yield colorless prisms. The
compound crystallizes in the monoclinic crystal system,
space group P 21/n, a = 8.2436(8) Å, b = 5.6026(6) Å, c =
1
3
3
7
5, 3350. (u) Singh, R. P.; Foxman, B. M.; Deng, L. J. Am. Chem.
Soc. 2010, 132, 9558. (v) Ouairy, C.; Michel, P.; Delpech, B.; Crich,
D.; Marazano, C. J. Org. Chem. 2010, 75, 4311. (w) Chen, Y.-F.;
Wang, H.-F.; Wang, Y.; Luo, Y.-C.; Zhu, H.-L.; Xu, P.-F. Adv.
Synth. Catal. 2010, 352, 1163. (x) Rodriguez, A.; Moran, W. J.
Tetrahedron Lett. 2011, 52, 2605. (y) Chang, M.-Y.; Cheng, Y.-J.;
Lu, Y.-J. Org. Lett. 2015, 17, 1264.
2
2
(
4) For DBU, see: (a) Reddy, C. R.; Reddy, M. D. J. Org. Chem. 2014,
79, 106. (b) Arcadi, A.; Cerichelli, G.; Chiarini, M.; Di Giuseppe, S.;
Marinelli, F. Tetrahedron Lett. 2000, 41, 9195.
3
1
8.4028(18) Å, V = 848.96(15) Å , Z = 4, d
mg/cm , F(000) = 344, 2θ range 2.216~26.394 , R indices
all data) R1 = 0.1664, wR2 = 0.3523.
= 1.269
calcd
3
o
(
5) For NaH, see: Vieser, R.; Eberbach, W. Tetrahedron Lett. 1995, 36,
(
4
405.
n
(
6) For PBu
3
, see: (a) Kuroda, H.; Hanaki, E.; Kawakami, M.
Tetrahedron Lett. 1999, 40, 3753. (b) Kuroda, H.; Hanaki, E.; Izawa,
H.; Kano, M.; Itahashi, H. Tetrahedron 2004, 60, 1913.
Acknowledgments
(
7) For reviews on the cycloisomerization, see: (a) Hashmi, A. S. K.;
Buhrle, M. Aldrichim. Acta 2010, 43, 27. (b) Belmont, P.; Parker, E.
Eur. J. Org. Chem. 2009, 6075. (c) Li, Z.; Brouwer, C.; He, C. Chem.
Rev. 2008, 108, 3239. (d) Arcadi, A. Chem. Rev. 2008, 108, 3239. (e)
Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180. (f) Furstner, A.;
Davies, P. W. Angew. Chem. Int. Ed. 2007, 46, 3410.
The authors would like to thank the Ministry of Science
and Technology of the Republic of China for its financial
support (MOST 104-2113-M-037-012).
References and notes
(8) (a) Chang, M.-Y.; Cheng, Y.-J.; Lu, Y.-J. Org. Lett. 2014, 16, 6252.
(b) Chang, M.-Y.; Chen, Y.-C.; Chan, C.-K. Tetrahedron 2014, 70,
(
1) For reviews on synthesis of furans, see: (a) Kilroy, T. G.; O’Sullivan,
T. P.; Guiry, P. J. Eur. J. Org. Chem. 2005, 4929. (b) Lin, J.; Liu, S.;
Sun, B.; Niu, S.; Li, E.; Liu, X.; Xhe, Y. J. Nat. Prod. 2010, 73, 905.
8908. (c) Chang, M.-Y.; Lu, Y.-J.; Cheng, Y.-C. Tetrahedron 2015,
71, 1192. (d) Chang, M.-Y.; Cheng, Y.-C.; Lu, Y.-J. Org. Lett. 2015,
17, 1264. (e) Chang, M.-Y.; Lu, Y.-J.; Cheng, Y.-C. Tetrahedron
2015, 71, 6840. (f) Chang, M.-Y.; Cheng, Y.-J.; Lu, Y.-J. Org. Lett.
2015, 17, 3142.
(
c) Rodriguez, B.; de la Torre, M. C.; Jimeno, M. L.; Bruno, M.;
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37. (d) Hou, X. L.; Cheung, H. Y.; Hon, T. Y.; Kwan, P. L.; Lo, T.
8
(9) For recent synthesis of β-ketosulfones, see: (a) Pospisil, J.; Sato, H.;
J. Org. Chem. 2011, 76, 2269. (b) Sreedhar, B.; Rawat, V. S. Synlett
2012, 23, 413. (c) Kumar, A.; Muthyala, M. K. Tetrahedron Lett.
2011, 52, 5368. (d) Lu, Q.; Zhang, J.; Zhao, G.; Qi, Y.; Wang, H.;
Lei, W. J. Am. Chem. Soc. 2013, 135, 11481. (e) Tsui, G. C.;
Glenadel, Q.; Lau, C.; Lautens, M. Org. Lett. 2011, 13, 208. (f) Zhou,
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4
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(
3) For representative examples, see: (a) Liu, Y.; Song, F.; Liu, M.; Yan,

ACCEPTED MANUSCRIPT
Tetrahedron
7
6
+
A.; Matsui, T.; Ima, M.; Saito, T.; Murota, M.; Aratani, Y.; Kijima,
H.; Yamamoto, H.; Maruyama, T.; Ohuchida, S.; Nakai, H.; Toda, M.
Bioorg. Med. Chem. 2006, 14, 7121. (c) Wendt, M. D.; Geyer, A.;
McClellan, W. J.; Rockway, T. W.; Weitzberg, M.; Zhao, X.; Mantei,
R.; Stewart, K.; Nienaber, V.; Klinghofer, V.; Giranda, V. L. Bioorg.
Med. Chem. Lett. 2004, 14, 3069. (d) Bouhlel, A.; Curti, C.; Dumetre,
A.; Laget, M.; Crozet, M. D.; Azas, N.; Vanelle, P. Bioorg. Med.
Chem. 2010, 18, 7310.
2008, 73, 3650. For Cr , see: (d) Herndon, J. W.; Wang, H. J. Org.
Chem. 1998, 63, 4564.
(13) CCDC 1411958 (4h) and 1427183 (7) contain the supplementary
crystallographic data for this paper. This data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: 44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk).
(14) (a) Dai, L.-Z.; Shi, M. Tetrahedron Lett. 2008, 49, 6437. (b) Zou, X.;
Jia, X.; Wang, X.; Xie, G. Synth. Commun. 2007, 37, 1617. (c)
Katrizky, A, R.; Wang, Z.; Wang, M.; Wilkerson, C. R.; Hall, C. D.;
Akhmedov, N. G. J. Org. Chem. 2004, 69, 6617.
(
11) (a) Zhang, X.; Lu, Z.; Fu, C.; Ma, S. J. Org. Chem. 2010, 75, 2589.
(b) Balachari, D.; Quinn, L.; O’Doherty, G. A. Tetrahedron Lett.
1
1
1
1
999, 40, 4769. (c) Marshall, J. A.; DuBay, W. J. J. Org. Chem.
993, 58, 3435. (d) Marshall, J. A.; DuBay, W. J. J. Org. Chem.
994, 59, 1703. (e) (a) Marshall, J. A.; Sehon, C. A. J. Org. Chem.
997, 62, 4313.
Supplementary Material
3
+
(
12) Synthesis of vinylfurans, see: for Ir , (a) Sevov, C. S.; Hartwig, J. F.
+
+
Experimental procedure and scanned photocopies of NMR
(CDCl ) spectral data were supported.
J. Am. Chem. Soc. 2014, 136, 10625. For Au /Ag , see: (b) Zhang,
X.; Lu, Z.; Fu, C.; Ma, S. J. Org. Chem. 2010, 75, 2589. For Pd ,
see: (c) Aurrecoechea, J. M.; Durana, A.; Perez, E. J. Org. Chem.
2+
3