Stereoselective Synthesis of Vinyl Iodides through Copper(I)-Catalyzed Finkelstein-Type Halide-Exchange Reaction

Article abstract of DOI:10.1055/s-0036-1588988

An efficient method for the stereoselective synthesis of vinyl iodides is described. The reactions of vinyl bromides with potassium iodide proceed smoothly in the presence of a copper catalyst under mild reaction conditions to produce the corresponding vinyl iodides stereospecifically and in satisfactory to excellent yields.

Full text of DOI:10.1055/s-0036-1588988

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2017, 49, A–F
paper
A
de
X. Feng et al.
Paper
Synthesis
Stereoselective Synthesis of Vinyl Iodides through Copper(I)-
Catalyzed Finkelstein-Type Halide-Exchange Reaction
Xiujuan Feng*a
Catalytic halogen-exchange reaction
Haixia Zhanga
Cu2O, L-proline
Br
I
Wenbo Lua
KI
+
R
R
EtOH, 110 °C
Yoshinori Yamamotoa,b
Abdulrahman I. Almansourc
Natarajan Arumugamc
Raju Suresh Kumarc
Ming Bao*a
up to 92% yield
a State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
116023, P. R. of China
fengxiujuan@dlut.edu.cn
mingbao@dlut.edu.cn
b WPI-AIMR (WPI-Advanced Institute for Materials Research), Tohoku University,
Sendai 980-8577, Japan
c Department of Chemistry, College of Sciences, King Saud University, P.O. Box
2455, Riyadh 11451, Saudi Arabia
Received: 25.02.2017
Accepted after revision: 10.03.2017
Published online: 11.04.2017
and stereoselective conversion of alkynes to E-iodoalkenes
proceed smoothly under mild conditions via in situ hydro-
zirconation of alkynes with the Schwartz reagent HZrCp2Cl,
which is produced from the reaction of ZrCp2Cl2 with
iBu2AlH or LiAlH(OtBu)3. However, the use of a stoichiomet-
ric amount of expensive organozirconium reagent is im-
practical. The fourth method is the hydrogenolysis of diio-
doalkenes by the Uenishi procedure or Yamamoto proce-
dure (Scheme 1, d).7 This method allows the formation of
the Z-isomer as the major product, but the starting materi-
als are not readily available.8
DOI: 10.1055/s-0036-1588988; Art ID: ss-2017-h1816-op
Abstract An efficient method for the stereoselective synthesis of vinyl
iodides is described. The reactions of vinyl bromides with potassium io-
dide proceed smoothly in the presence of a copper catalyst under mild
reaction conditions to produce the corresponding vinyl iodides ste-
reospecifically and in satisfactory to excellent yields.
Key words stereoselective synthesis, vinyl iodides, vinyl bromides,
copper catalyst, halide-exchange reaction
Previous work
The development of convenient and efficient methods
for the synthesis of vinyl iodides has attracted considerable
attention. Vinyl iodides are widely used in various coupling
reactions as active electrophilic reagents to form carbon–
carbon and carbon–heteroatom bonds.1 In addition, I-radio-
labeled vinyl iodides can be used as radiopharmaceuticals,
which play an important role in the biomedical field as pos-
itron emission tomography agents for serotonin transporter
imaging.2 Over the past few decades, four main methods
have been developed for the synthesis of vinyl iodides. The
first method is the well-known Wittig reaction, which al-
lows the formation of a mixture of Z- and E-isomers
(Scheme 1, a).3 The second method is the Takai reaction
(Scheme 1, b),4 which is frequently employed in multistep
total synthesis.5 However, this efficient method still has
some disadvantages, such as the generation of a mixture of
Z- and E-isomers and the use of large amounts of toxic
chromium(II) chloride. The third method is the hydrozir-
conation–iodinolysis of alkynes (Scheme 1, c).6 The regio-
(Ph3P+CH2I) I–, base
RCHO
RCHO
(a)
(b)
R
I
Wittig reaction
CHI3, CrCl2
I
R
Takai reaction
ZrCp2Cl2
iBu2AlH or LiAlH(OtBu)3
R
H
H(Me)
ZrLn
R
H
H(Me)
I
I2
iodinolysis
R
H(Me)
(c)
(d)
hydrozirconation
Uenishi procedure: cat. Pd(PPh3)4, Bu3SnH
or Yamamoto procedure: Zn-Cu, AcOH
I
Ph
Ph
hydrogenolysis
I
I
This work
cat. Cu2O, L-proline
KI
I
Br
+
(e)
R
R
EtOH, 110 °C
catalytic halide-exchange reaction
Scheme 1 Synthetic methods for the preparation of vinyl iodides
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–F

B
X. Feng et al.
Paper
Synthesis
Recently, the Finkelstein-type halide-exchange reaction
for the synthesis of aryl and heteroaryl iodides has attract-
ed considerable interest.9 This process offers several advan-
tages, such as mild conditions, broad substrate scope, and
high yield. To date, however, limited reports have been
available on the synthesis of vinyl iodides by the catalytic
Finkelstein-type halide-exchange reaction. Only 2-iodo-3-
methylbut-2-ene has been reported to be obtained through
a copper-catalyzed Finkelstein-type halide-exchange reac-
tion (Scheme 2, a).9k In addition, only (E)-(2-bromovi-
nyl)benzene has been reported to be converted into the
corresponding vinyl iodide via a photo-induced metal-cata-
lyst-free procedure (Scheme 2, b); poor stereoselectivity
(Z/E = 1.7:1) was observed.10 On the basis of known reports,
it appears that the synthesis of vinyl iodides by means of
copper-catalyzed Finkelstein-type halide-exchange reac-
tion has not been studied systematically thus far; the ste-
reoselectivity in the copper-catalyzed Finkelstein-type
vinyl halide-exchange reaction has not been revealed.
tivity (entry 6, 85% yield). No reaction was observed in the
absence of a ligand (entry 1). The ligands (Figure 1) were
then screened while Cu2O and KI were used as the catalyst
and iodine source, respectively (entries 14–20). Only trace
amounts of the desired product, (E)-β-iodo-4-methylsty-
rene (2b), was observed when the ligand pyridine (L2) was
examined (entry 14). When the ligands N1,N1,N2,N2-te-
tramethylethane-1,2-diamine (L3) and pyridine-2,6-dicar-
boxylic acid (L4) were examined, the desired product 2b
was obtained in 20% and 19% yield, respectively (entries 15
and 16). Iodide 2b was obtained in 72–87% yield when eth-
ane-1,2-diamine (L5), L-proline (L6), 2,2-bipyridine (L7),
and 1,10-phenanthroline (L8) were used as ligands (entries
17–20). Among the ligands examined, L6 proved to be the
most effective (entry 18, 87% yield). The iodine sources, in-
Table 1 Reaction Conditions Screeninga
Br
I
cat. Cu, ligand
I source
+
EtOH, 110 °C, 24 h
CuI (5.0 mol%)
MeHNCH2CH2NHMe (10 mol%)
2b
Me
Me
Me
I
1b
Me
Me
Me
Br
NaI (1.5 equiv)
(a)
(b)
nBuOH, 120 °C, 24 h
Entry
Cu salt (mol%)
Ligand
I source
Yield (%)b
76% yield
1
2
CuI (20)
none
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
L7
L8
L6
L6
KI
NRc
72
Br
I
I2 (10 mol%), NaI (2.0 equiv)
MeCN, UV, r.t., argon, 18 h
CuI (20)
KI
3
CuBr (20)
CuCl (20)
CuCN (20)
Cu2O (10)
CuF2 (20)
KI
38
63% yield (Z/E = 1.7:1)
4
KI
40
Scheme 2 Reported examples of vinyl iodide synthesis
5
KI
83
6
KI
85
We have recently reported facile aryl bromide–chloride
and aryl bromide–iodide exchange reactions by using Cu2O
and Me4NCl/KI as the catalyst and the chlorine/iodine
source, respectively. These reactions were successfully car-
ried out via the Finkelstein-type halide-exchange reaction
to produce aryl and heteroaryl chlorides or aryl and het-
eroaryl iodides in good to excellent yields.11 This successful
study encouraged us to conduct a study as to whether vinyl
iodides can also be stereoselectively synthesized through
the copper-catalyzed Finkelstein-type halide-exchange re-
action. As expected, the target reaction proceeded smooth-
ly under optimized conditions with stereospecificity. The
results are reported in the present work (Scheme 1, e).
In the initial studies conducted, the halogen-exchange
reaction of (E)-β-bromo-4-methylstyrene (1b) was chosen
as a model to optimize the reaction conditions. The results
are shown in Table 1. The copper catalyst significantly in-
fluenced the stereoselective synthesis of vinyl iodide 2b.
Several Cu(I) salts (CuI, CuBr, CuCl, CuCN, Cu2O) and Cu(II)
salts [CuF2, Cu(acac)2, CuCl2, Cu(OAc)2, CuSO4, Cu(NO3)2,
CuO] were initially tested in ethanol at 110 °C in the pres-
ence of picolinic acid (L1) and KI as ligand and iodine
source, respectively (entries 2–13).12 Among the Cu(I) and
Cu(II) salts tested, Cu2O exhibited the highest catalytic ac-
7
KI
trace
29
8
Cu(acac)2 (20)
CuCl2 (20)
Cu(OAc)2 (20)
CuSO4 (20)
Cu(NO3)2 (20)
CuO (20)
KI
9
KI
trace
trace
trace
trace
trace
trace
20
10
11
12
13
14
15
16
17
18
19
20
21
22
KI
KI
KI
KI
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
KI
KI
KI
19
KI
75
KI
87
KI
81
KI
72
Me4NI
NaI
trace
60
a Reaction conditions: 1b (1.0 mmol), iodine source (2.0 equiv), Cu salt, li-
gand (20 mol%), EtOH (3.0 mL), sealed tube.
b Yield determined by 1H NMR; dibromomethane used as internal standard.
c NR = no reaction.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–F

C
X. Feng et al.
Paper
Synthesis
cluding KI, Me4NI, and NaI, were finally screened, with KI
proving to be the best iodine source (entry 18 vs. entries 21
and 22). Therefore, the optimized conditions consist of the
use of KI as iodine source, Cu2O as precatalyst, and L6 as li-
gand, in EtOH at 110 °C for 24 hours.
Table 2 Copper(I)-Catalyzed Vinyl Bromide–Iodide Exchange Reac-
tionsa
I
Br
Cu2O, L-proline
KI
+
R
R
EtOH, 110 °C, 24 h
2a–i
1a–i
N
N
N
HOOC
N
COOH
N
COOH
NH2
Entry
1
Bromide 1 Iodide product 2
Yield (%)b
82
L4
L1
L5
L2
L3
L7
I
1a
2a
COOH
H2N
N
H
N
N
N
N
I
L6
L8
2
3
4
5
6
7
8
1b
2b
2c
2d
2e
2f
87
84
92
91
77
81
67
Figure 1
I
I
1c
The reactions of vinyl bromides 1a–i with KI were per-
formed under the optimized conditions, and the results are
summarized in Table 2. The reaction of (E)-β-bromostyrene
(1a) efficiently proceeded to produce the corresponding
product, (E)-β-iodostyrene (2a), in good yield (82%; entry
1). (E)-β-Bromo-4-methylstyrene (1b) and (E)-β-bromo-4-
methoxystyrene (1c) bearing electron-donating groups on
the benzene ring exhibited almost the same reactivity as
substrate 1a, to form the corresponding vinyl iodides 2b
and 2c in good yields (87% and 84%, respectively; entries 2
and 3). (E)-β-Bromo-3,4-dimethoxystyrene (1d) and (E)-β-
bromo-3,4-methylenedioxystyrene (1e), each bearing two
electron-donating groups on the benzene ring, exhibited
higher reactivity than that of substrates 1a–c, to produce
the corresponding vinyl iodides 2d and 2e in excellent
yields (92% and 91%, respectively; entries 4 and 5). Sub-
strates 1f–i bearing halogen atoms F and Cl on the benzene
rings also underwent the bromide–iodide exchange reac-
tion smoothly to give vinyl iodides 2f–i in satisfactory to
good yields (67%–81% yields, entries 6–9). These results in-
dicate that the reaction yield was moderately affected by
the electronic property of the substituent linked to the ben-
zene ring of the substrate; the substrates bearing an elec-
tron-donating group on the benzene ring showed a slightly
higher reactivity. Notably, the F and Cl atoms linked to the
aromatic ring were retained in the structures of vinyl io-
dides 2 under the halogen-exchange reaction conditions,
thus suggesting that further manipulation may produce
useful compounds.
MeO
MeO
1d
MeO
I
O
1e
O
I
1f
F
I
1g
2g
2h
Cl
Cl
I
1h
Cl
I
9
1i
2i
74
a Reaction conditions: 1a–i (1.0 mmol), KI (2.0 equiv), Cu2O (10 mol%), L6
(20 mol%), EtOH (3.0 mL), sealed tube, 110 °C, 24 h.
b Isolated yield.
couraged us to study alkylvinyl bromide–iodide exchange
reactions. As expected, the reactions of (4-bromobut-3-en-
1-yl)benzene (1l) and (4-bromobut-3-en-2-yl)benzene
(1m) with KI proceeded smoothly to produce the desired
products, (4-iodobut-3-en-1-yl)benzene (2l) and (4- io-
dobut-3-en-2-yl)benzene (2m), in 94% and 71% yields, re-
spectively, with the same Z/E ratio as the starting materials
(Scheme 3, c and d). These results indicate that the Z- and E-
isomers of the bromide substrates were exclusively con-
verted into the Z- and E-isomers of iodide products, respec-
tively. Thus, the scope of the copper-catalyzed Finkelstein-
type bromide–iodide exchange reaction could be expanded
to heteroarylvinyl bromides and alkylvinyl bromides. No
reaction was observed when (E)-(2-chlorovinyl)benzene
(1n) was examined (Scheme 3, e). A mixture of (E)-1-iodo-
The reaction of (Z)-β-bromostyrene (1j) was investigat-
ed, and the corresponding product (Z)-β-iodostyrene (2j)
was obtained in good yield (83%) with 100% stereoselectivi-
ty (Scheme 3, a). Interestingly, the reaction of 2-(2-bromov-
inyl)furan (1k) with KI also proceeded smoothly to produce
the desired product, 2-(2-iodovinyl)furan (2k) in 66% yield;
the same ratio of Z-isomer to E-isomer (1:1) was observed
in bromide 1k and iodide 2k (Scheme 3, b). The successful
acquisition of arylvinyl (and heteroarylvinyl) iodides by
copper-catalyzed bromide–iodide exchange reactions en-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–F

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X. Feng et al.
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Synthesis
3-(2-iodovinyl)benzene, (E)-1-(2-bromovinyl)-3-iodoben-
zene, and (E)-1-bromo-3-(2-iodovinyl)benzene was ob-
tained when (E)-1-bromo-3-(2-bromovinyl)benzene (1o)
was treated under the optimum conditions (Scheme 3, f).
1,1,2-Tribromoethene (1p), a multiply bromo-substituted
substrate, was finally tested. A complex mixture that could
not be separated was obtained (Scheme 3, g).
O
Cu2O
+
N
H
OH
– H2O
O
I
Br
N
H
O
R
R
Cu
1
2
A
Cu2O, L-proline
KI
+
(a)
I
Br
EtOH, 110 °C, 24 h
O
O
O
O
2j, 83% yield
1j
N
H
N
Cu2O, L-proline
H
Cu
Cu
I
Br
+
KI
(b)
EtOH, 110 °C, 24 h
O
O
I
Br
R
R
2k
1k
Z/E = 1:1
C
B
66% yield (Z/E = 1:1)
I
Br
Cu2O, L-proline
KI
KBr
KI
+
(c)
(d)
EtOH, 110 oC, 24 h
Scheme 4 Proposed mechanism
1l
2l
Z/E = 3:1
94% yield (Z/E = 3:1)
In conclusion, for the first time we have systematically
researched the copper-catalyzed vinyl bromide–iodide ex-
change reaction. This Finkelstein-type halogen-exchange
reaction proceeds in a highly stereospecific manner; the
double bond configuration of the bromide substrates is re-
tained in the iodide products. The current work provides a
practical and green procedure for stereoselective synthesis
of vinyl iodide compounds from readily available vinyl bro-
mides13 and from an inexpensive iodine source.
Cu2O, L-proline
I
+
KI
Br
EtOH, 110 oC, 24 h
1m
Z/E = 1:1
2m
71% yield (Z/E = 1:1)
Cl
Cu2O, L-proline
+
KI
No reaction
(e)
EtOH, 110 °C, 24 h
1n
I
I
+
+
Solvents were dried and degassed before use by standard procedures.
1H NMR spectra were recorded on either a Varian Inova-400 spec-
trometer (400 MHz for 1H, 100 MHz for 13C) or a Bruker Avance II-400
spectrometer (400 MHz for 1H, 100 MHz for 13C); CDCl3 and TMS were
used as solvent and internal standard, respectively. High-resolution
mass spectra were recorded on a UPLC-Q-TOF mass spectrometer. GC-
MS analyses were performed on an Agilent 7890A-5975C instrument.
TLC was carried out on silica gel 60 (200–300 mesh), and the spots
were located with UV light. Melting points were determined by using
a micro-melting-point apparatus and are uncorrected.
Br
Br
I
Br
Cu2O, L-proline
+
KI
(f)
EtOH, 110 °C, 24 h
1o
Br
I
Br
Br
Br
Cu2O, L-proline
+
KI
Complex mixture
(g)
EtOH, 110 °C, 24 h
H
1p
Vinyl Bromide–Iodide Exchange Reaction; Typical Procedure
Scheme 3 Conversion of other vinyl bromides into the corresponding
A Schlenk tube was charged with Cu2O (14.3 mg, 0.1 mmol), L-proline
(23.0 mg, 0.2 mmol), vinyl bromide 1a–m (1.0 mmol), KI (332 mg, 2.0
mmol), and anhyd EtOH (3.0 mL) under a N2 atmosphere. The Schlenk
tube was sealed with a Teflon valve, and then the reaction mixture
was stirred at 110 °C for 24 h. After the reaction was completed, the
solvent was removed under reduced pressure. The residue obtained
was purified by chromatography (silica gel, PE–EtOAc, 50:1) to pro-
duce the corresponding vinyl iodide 2a–m.
iodides
A plausible mechanism for the copper-catalyzed vinyl
bromide–iodide exchange reaction is shown in Scheme 4.
The interaction between L-proline and Cu2O generates a
Cu(I) complex A. Oxidative addition of 1 to Cu(I) species A
produces intermediate B. The halogen-exchange reaction
between B and KI generates intermediate C, which subse-
quently undergoes reductive elimination to produce vinyl
iodide 2 and to regenerate Cu(I) catalyst A.
(E)-β-Iodostyrene (2a)14
Yellow oil; yield: 188.6 mg (82%).
1H NMR (400 MHz, CDCl3): δ = 7.43 (d, J = 14.8 Hz, 1 H), 7.34–7.26 (m,
5 H), 6.83 (d, J = 14.8 Hz, 1 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–F

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X. Feng et al.
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Synthesis
(E)-β-Iodo-4-methylstyrene (2b)14
13C NMR (500 MHz, CDCl3): δ = 143.59, 139.32, 134.71, 129.95,
128.35, 125.96, 124.20, 78.62.
White solid; mp 81–82 °C; yield: 212.3 mg (87%).
1H NMR (400 MHz, CDCl3): δ = 7.38 (d, J = 14.8 Hz, 1 H), 7.19–7.17 (m,
2 H), 7.12 (d, J = 8.4 Hz, 2 H), 6.74 (d, J = 14.8 Hz, 1 H), 2.32 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.85, 138.40, 135.04, 129.43,
GC-MS: tR (min) = 9.288; m/z = 263.9 [M].
(E)-2-Chloro-β-iodostyrene (2i)17
Yellow oil; yield: 195.7 mg (74%).
125.94, 75.46, 21.37.
1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 14.8 Hz, 1 H), 7.41–7.32 (m,
2 H), 7.24–7.19 (m, 2 H), 6.88 (d, J = 14.8 Hz, 1 H).
GC-MS: tR (min) = 11.037; m/z = 244.0 [M].
(E)-β-Iodo-4-methoxystyrene (2c)15
White solid; mp 96–97 °C (Lit.15 mp 98–99 °C); yield: 218.5 mg (84%).
(Z)-β-Iodostyrene (2j)19
Yellow oil; yield: 190.9 mg (83%).
1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 6.8 Hz, 2 H), 7.38–7.31 (m, 3
H), 7.28 (d, J = 8.8 Hz, 1 H), 6.53 (d, J = 8.8 Hz, 1 H).
1H NMR (400 MHz, CDCl3): δ = 7.35 (d, J = 15.2 Hz, 1 H), 7.23 (dd, J =
6.4, 1.6 Hz, 2 H), 6.84 (dd, J = 6.8, 2.0 Hz, 2 H), 6.62 (d, J = 14.8 Hz, 1 H),
3.80 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 159.74, 144.31, 130.71, 127.29,
114.08, 73.63, 55.34.
2-(2-Iodovinyl)furan (2k)20
Yellow oil; yield: 145.2 mg (66%).
GC-MS: tR (min) = 12.495; m/z = 260.0 [M].
1H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 1.6 Hz, 1 H), 7.36–7.33 (m, 2
H), 7.17 (d, J = 14.8 Hz, 1 H), 7.16 (d, J = 3.6 Hz, 1 H), 6.71 (d, J = 14.8
Hz, 1 H), 6.48–6.46 (m, 1 H), 6.41 (d, J = 8.8 Hz, 1 H), 6.35–6.33 (m, 1
H), 6.23 (d, J = 3.2 Hz, 1 H).
(E)-β-Iodo-3,4-dimethoxystyrene (2d)16
White solid; mp 99–100 °C; yield: 266.9 mg (92%).
1H NMR (400 MHz, CDCl3): δ = 7.34 (d, J = 14.8 Hz, 1 H), 6.85–6.79 (m,
3 H), 6.64 (d, J = 14.8 Hz, 1 H), 3.87 (d, J = 3.2 Hz, 6 H).
13C NMR (100 MHz, CDCl3): δ = 149.40, 149.02, 144.53, 130.92,
119.38, 110.96, 108.26, 73.93, 55.94, 55.87.
(4-Iodobut-3-enyl)benzene (2l)21
Colorless oil; yield: 241.9 mg (94%).
1H NMR (400 MHz, CDCl3): δ = 7.30–7.13 (m, 10 H), 6.56–5.98 (m, 4
H), 2.74–2.66 (m, 4 H), 2.54–2.43 (m, 3 H), 2.34 (q, J = 7.6, 1 H).
HRMS: m/z [M]+ calcd for C10H11IO2: 289.9802; found: 289.9804.
(E)-β-Iodo-3,4-methylenedioxystyrene (2e)17
(3-Iodo-1-methylprop-2-enyl)benzene (2m)20
White solid; mp 75–76 °C; yield: 249.4 mg (91%).
1H NMR (400 MHz, CDCl3): δ = 7.31 (d, J = 14.8 Hz, 1 H), 6.81 (d, J = 0.8
Hz, 1 H), 6.75–6.74 (m, 2 H), 6.61 (d, J = 14.8 Hz, 1 H), 5.96 (s, 2 H).
Colorless oil; yield: 182.4 mg (71%).
1H NMR (400 MHz, CDCl3): δ = 7.30–7.15 (m, 10 H), 6.70–6.65 (m, 1
H), 6.25–6.12 (m, 2 H), 6.02 (d, J = 14.4 Hz, 1 H), 3.86–3.79 (m, 1 H),
3.48–3.41 (m, 1 H), 1.37–1.33 (m, 6 H).
13C NMR (100 MHz, CDCl3): δ = 148.09, 147.87, 144.37, 132.24,
121.00, 108.33, 105.27, 101.33, 74.28.
HRMS: m/z [M]+ calcd for C9H7IO2: 273.9489; found: 273.9491.
Acknowledgment
(E)-4-Fluoro-β-iodostyrene (2f)14
We are grateful to the National Natural Science Foundation of China
(Nos. 21373041, 21372035 and NSFC-IUPAC program, No.
21361140375) for their financial support. The authors extend their
appreciation to the International Scientific Partnership Program ISPP
at King Saud University for funding this research work through
ISPP#0048.
Yellow oil; yield: 191.0 mg (77%).
1H NMR (400 MHz, CDCl3): δ = 7.38 (d, J = 14.8 Hz, 1 H), 7.28–7.24 (m,
2 H), 7.03–6.98 (m, 2 H), 6.75 (d, J = 14.8 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 162.68 (d, J = 247 Hz), 143.71, 133.98
(d, J = 4 Hz), 127.66 (d, J = 8 Hz), 115.75 (d, J = 22 Hz), 76.22 (d, J = 2
Hz).
GC-MS: tR (min) = 9.984; m/z = 248.0 [M].
Supporting Information
(E)-4-Chloro-β-iodostyrene (2g)14
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0036-1588988.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
o
nrtogI
f
rmoaitn
Yellow oil; yield: 214.2 mg (81%).
1H NMR (400 MHz, CDCl3): δ = 7.38 (d, J = 14.8 Hz, 1 H), 7.30–7.27 (m,
2 H), 7.23–7.20 (m, 2 H), 6.84 (d, J = 14.8 Hz, 1 H).
References
(E)-3-Chloro-β-iodostyrene (2h)18
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–F

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