Ready access to organoiodides: Practical hydroiodination and double-iodination of carbon-carbon unsaturated bonds with I2

Article abstract of DOI:10.1016/j.tet.2019.05.019

By using I₂ or I₂/H₃PO₃ system, various alkenes and alkynes were converted to the corresponding alkyl and alkenyl iodides in good yields. In the presence of I₂, alkynes could be di-iodinated using H₂O as the solvent in air at room temperature. This method also features the simple work-up procedure since the pure product could be obtained by extraction. Additionally, for the first time, combining with the non-toxic and cheap phosphonic acid H₃PO₃, alkenes and alkynes were also hydroiodinated successfully, which provides a simple and practical approach for synthesis of organoiodides.

Full text of DOI:10.1016/j.tet.2019.05.019

Accepted Manuscript
Ready access to organoiodides: Practical hydroiodination and double-iodination of
carbon-carbon unsaturated bonds with I
2
Jing Xiao, Li-Biao Han
PII:
S0040-4020(19)30538-1
DOI:
https://doi.org/10.1016/j.tet.2019.05.019
TET 30340
Reference:
To appear in: Tetrahedron
Received Date: 26 March 2019
Revised Date: 26 April 2019
Accepted Date: 8 May 2019
Please cite this article as: Xiao J, Han L-B, Ready access to organoiodides: Practical hydroiodination
and double-iodination of carbon-carbon unsaturated bonds with I , Tetrahedron (2019), doi: https://
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doi.org/10.1016/j.tet.2019.05.019.
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Ready Access to Organoiodides: Practical
Hydroiodination and Double-Iodination of
Carbon-Carbon Unsaturated Bonds with I2
Leave this area blank for abstract info.
Jing Xiaoa,b and Li-Biao Hanb,c*
aKey Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School
of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201,
China.
bNational Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
cInstitute of Drug Discovery Technology, Ningbo University, Ningbo, Zhejiang 450052, China

1
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Tetrahedron
journal homepage: www.elsevier.com
Ready access to organoiodides: practical hydroiodination and double-iodination of
carbon-carbon unsaturated bonds with I2
Jing Xiaoa, b and Li-Biao Hanb,c
aKey Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan
University of Science and Technology, Xiangtan 411201, China
bNational Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
cInstitute of Drug Discovery Technology, Ningbo University, Ningbo, Zhejiang 450052, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
By using I2 or I2/ H3PO3 system, various alkenes and alkynes were converted to the
corresponding alkyl and alkenyl iodides in good yields. In the presence of I2, alkynes could be
di-iodinated using H2O as the solvent in air at room temperature. This method also features the
simple work-up procedure since the pure product could be obtained by extraction. Additionally,
for the first time, combining with the non-toxic and cheap phosphonic acid H3PO3, alkenes and
alkynes were also hydroiodinated successfully, which provides a simple and practical approach
for synthesis of organoiodides.
Available online
Keywords:
Organoiodides
Hydroiodination
Double-iodination
Iodine
2019 Elsevier Ltd. All rights reserved
.
phosphonic acid
———
Corresponding author. Tel.: +81-298-61-4855; fax: 81-29-861-6344; e-mail: libiao-han@aist.go.jp

2
Tetrahedron
ACCEPTED MANUSCRIPT
1. Introduction
H3PO3/I2, phenylacetylene 1a was hydroiodinated smoothly to
afford the Markovnikov-type alkyl iodides in 90% yield (2a).
Similarly, selected examples for hydroiodination of aryl olefins
were also given, and indicated that substituents such as Me, F, Cl,
Br and CF3 were well tolerable under the reaction conditions (2b-
2f). Aliphatic alkenes, terminal alkene 1g oct-1-ene and internal
alkene 1h (E)-oct-4-ene, also gave 94% and 93% yields of the
products, respectively (2g and 2h). By slightly tuning the
reaction conditions, cyclooctene 1i also gave a moderate yield of
the product (2i).
Organic iodide is one of the most useful chemicals in organic
synthesis because of its high reactivity compared to their chloro
and bromo counterparts.1 Herein we report a ready access to
these useful compounds, iodoalkanes 1, iodoalkenes 2 and 1,2-
diiodoalkens 3, by using elemental iodine I2 via simple and
practical hydroiodination and double-iodination of the readily
available alkenes and alkynes, respectively (Scheme 1). Thus, in
the presence of phosphonic acid, hydroiodination took place
readily with alkenes and alkynes to produce the corresponding
iodoalkanes 1 (Scheme 1 (a)) and iodoalkenes 2 (Scheme 1 (b)),
respectively, in high yields. On the other hand, in the absence of
phosphonic acid, double iodination occurs with alkynes to give
the corresponding 1,2-diiodoalkens 3 in high yields (Scheme 1
(c)).
Table 1. Hydroiodination of alkenes with I2 / H3PO3 system.a
Although there are several methods developed for the
synthesis of organic iodides, the direct addition of HI
(hydroiodination) to the easily available alkenes and alkynes is
apparently is the most straightforward method. However, this
method often suffers from drawbacks such as poor yields and
side reactions due to the rather difficultly controllable iodine
liberation problem of the unstable HI.2 Therefore, instead of
employing hydrogen iodide HI, alter-native reagents that
generate HI in situ have been used, such as H2/I2/Rh,3 I2/Al2O3,4
CuO·HBF4/I2/Et3SiH,5
I2/thiol,8 Me3SiCl/NaI,9
TiI4,6
Polymethylhydrosiloxane/I2,7
aReaction conditions: 0.3 mmol 1, 0.18 mmol I2, 0.6 mmol H3PO3
in 1.5 mL EtOAc at 80 oC for 45 minutes. Isolated yield based on
alkynes. bBenzene 0.3 mL for 13 minutes. c0.225 mmol I2 and 0.3
mL EtOAc were used, 100 oC, 20 h. d0.15 mmol I2 and 0.9 mmol
o
alkyenes were used in 100 C for 22 h. Isolated yield based on
iodine atom.
Scheme 1. Selective generation of organic iodides with elemental
iodine.
The value of this I2 / H3PO3 system lies further on its ability to
hydroiodination of alkynes. Thus, a series of hydroiodination
reactions were conducted and the results were combined in table
2. Phenylacetylene 3a underwent this hydroiodination with
excellent selectivity to yield the Markovnikov-type adduct 4a in
85% yields based on iodine atom. When 1.0 equivalent alkynes
such as arylethynes bearing methyl and tert-bultyl were
employed, the iodination also took place to give the
corresponding product in good yield (4b and 4c). Worth noting is
that arylethynes with electron-withdrawing group such as Cl, F,
and CF3 all could be hyrdroiodinated to the corresponding
iodoalknenes in morderate to good yields (4d-4f). 1-
Ethynylnaphthalene 3g served as a good substrate in this reaction
to produce Markovnikov-type product in 87% yield (4g). In the
case of internal alkyne 1,2-diphenylethyne 3h, the iodination
proceeded smoothly, producing the (E)-olefin product in good
yield (4h). It should be noted that aliphatic alkyne 3i could also
give high yield of the product under the present reaction
conditions (4i).
CeCl3·7H2O/NaI.10 A Ph2P(O)H/I2 system that may be closely
related to the current work was also disclosed by Ogawa et al.11
However, Ph2P(O)H is a rather expensive chemical and the
preparation of an organoiodide using Ph2P(O)H is too expensive.
As a by-product, a large amount of phosphonic acid (H3PO3)
was generated from our ongoing project. Phosphonic acid is a
low-toxic, common and cheap chemical. However its utility was
rather unexploited. For example, it was estimated that million
tons of phosphonic acid was generated every year as the by-
product from the preparation of RC(O)Cl using PCl3 and the
process of the electroless nickle plating using H3PO2. However,
most of these phosphonic acid was disposed as waste. Since
H3PO3 has a potentially reactive P(O)H bond, we expected that
this compound might serve as a green H source for reduction. In
an effort to develop simple and green synthetic methodologies,
we are attracted by the potential using H3PO3 as the hydrogen
source for hydroiodination of unsaturated bonds, since no
examples were reported using H3PO3 as a hydrogen source for
hydroiodination so far. In addition, as described above, H3PO3
was readily available, cheap and low-toxic. The present I2/H3PO3
combination has the advantage that avoiding use metals and
expensive materials comparing to the literature methods.3-11
Table 2. Hydroiodination of alkynes with I2 / H3PO3 system.a
2. Results and Discussion
We initiated our research by carrying out the hydroiodination
of alkenes. As demonstrated in table 1, in the presence of

3
R2
I
I
ACCEPTED MANUSCRIPT
R1
I2
+
R1
R2
+
R1
I2
H3PO3
+
I
R1
3
5
3
4
I
I
I
I
I
I
I
I
I
I
I
MeO
t-Bu
5d
5c
5b
5a
t-Bu
97%, E/Z=98/2
95%, E/Z=94/6
92%, E/Z > 99/1
98%, E/Z > 99/1
b
4b
I
4a
: 85%
: 79%
4c
I
I
: 75%
I
I
I
I
I
I
I
I
Ac
Cl
F3C
OHC
5h
5e
5f
5g
99%b, E/Z > 99/1
98%b, E/Z > 99/1
99%b, E/Z > 99/1
98%b, E/Z > 99/1
Cl
F
F3C
I
I
I
b
b,c
4e
I
4d
: 80%
: 55%
4f
: 56%
I
I
I
I
I
5k
5j
5i
99%, E/Z=98/2
95%b, E/Z > 99/1
N.D.
aReaction conditions: 0.3 mmol 3, 0.375 mmol I2, 1.0 mL H2O,
R.T., 3 h. Isolated yield based on alkynes. E/Z ratio was
determined by GC-MS. b22 h.
4i
: 89%
4g
: 87%
4h
: 89%
aReaction conditions: 0.3 mmol 3, 0.15 mmol I2, 0.9 mmol H3PO3
in 1.5 mL CH3CN at 80 C for 15 minutes. Isolated yield based
on alkynes. 0.15 mmol I2, 0.9 mmol alkynes were used. Isolated
o
Decreasing the temperature from 60 oC to room temperature,
product 5a could also be obtained in good yield (entry 2). By
further prolonging the reaction time and increase the amount of I2
good results (entry 3 and 4) were obtained. During screening the
solvents, we are delighted to find that H2O performed the best
among other solvents such as CH2Cl2, CH3CN, and EtOAc (entry
5-8). Encouraged by the above results, we next examined the
reaction under air, and found that phenylacetylene 3a could be
readily di-iodinated by I2 in excellent yield (entry 9).
b
yield based on iodine atom. c3 h.
During the above-mentioned studies of HI addition with
alkyne, we found that interestingly, when the reaction was
conducted in the absence of H3PO3, selective double-iodination
took place to produce the corresponding 1,2-diioalkens in high
yields. 1,2-diiodoalkenes are key intermediates in cross coupling
reactions for constructing complex molecules since they possess
two highly reactive sites.2 Literature searches revealed that
Having optimized the reaction conditions, we next explored
the substrate scope of this iodination reaction. As summarized in
Table 4, various functionalized alkynes having diverse groups on
the aromatic ring were well tolerated in this system. The electron-
donating arylethynes bearing methyl, tert-bultyl and OMe groups
in the para-position of benzene ring were compatible under this
reaction conditions, generating the corresponding (E)-
diiodoalkenes in high yields with excellent stereoselectively (5b–
5d). By prolonging the reaction time, substrates with electron-
withdrawing groups such as Cl, CF3, CHO and C(O)Me on the
benzene ring were also double-iodinated successfully, furnishing
the products in excellent yields (5e–5h). 1-Ethynylnaphthalene
was also applicable to this iodination reaction, giving the desired
several procedures toward 1,2-diiodoalkenes including CuI/I2,12
PhI(OAc)2/ I−
,
I2/Al2O3,14 ICl/I−,15 H2O2/I2 etc. Although a few
13
examples were found with this double-iodination by using iodine
only,17 a simpler, greener, and more practical method for their
preparation are clearly desirable.
As shown in table 3, under N2, phenylacetylene 3a was mixed
with 1.0 equivalent I2 and stirred in benzene at 60 C for 1 hour
gave 92% yield of (E)-(1,2-diiodovinyl)benzene 5a (entry 1).
Table 3. Optimization of the reaction conditions.a
o
I
I2
I
+
I
I2
3a
5a
+
I
H2O, R.T.
5a
time
yieldb
entry
solvent
benzene
benzene
benzene
benzene
CH2Cl2
CH3CN
EtOAc
H2O
temp.
60 oC
R.T.
R.T.
R.T.
R.T.
R.T.
R.T.
R.T.
R.T.
I2 (equiv.)
3a: 5 mmol
97% yield
1.73 g
1
2
3
4
5
6
7
8
9c
1.0
1.0
1 h
1 h
3 h
3 h
3 h
3 h
3 h
3 h
3 h
92%
83%
88%
97%
82%
96%
81%
98%
98%
1.0
1.25
1.25
1.25
1.25
1.25
1.25
H2O
aReaction conditions: 3a (0.3 mmol) and I2 stirred in a solvent
b
(1.0 mL) under N2. GC yield based on 3a using n-decane as an
internal standard. cUnder air.
Scheme 2. Scale-up reaction.
Table 4. Double-iodination of alkynes with I2.a
product 5i in a nearly quantitative yield. It is worth noting that
ali-phatic alkynes also work efficiently under the current

4
Tetrahedron
conditions, producing the expected product in 95% yield (5j).
spectroscopy were recorded on a JEOL JNM-ECS400 (400 MHz
ACCEPTED MANUSCRIPT
However, when 1,2-diphenylethyne was used as the substrate, no
addition took place as confirmed by GC-MS and the 1,2-
diphenylethyne was recovered (5k).
for 1H and 100 MHz for 13C) in CDCl3. The coupling constants J
1
are given in Hz. Chemical shifts for H NMR are referred to
internal Me4Si (0 ppm). GC-MS were conducted on a Shimadzu
GCMS-QP2010 plus equipped with EI ion source.
To probe the scalability of this iodination reaction, a gram-
scale reaction was conducted. Thus, phenylacetylene 3a and
powder I2 were charged in the bottle, and 10 mL H2O was added
then. Because of the relatively poor solubility of I2 and
phenylacetylene in H2O, 1mL CH3CN was added into the
reaction mixture. The mixture was vigorously stirred for 46 hours
at room temperature. As illustrated in scheme 2, the product was
precipitated on the bottom after the reaction (scheme 2, pic a). To
remove excess I2, 5.0 wt% Na2S2O3 aqueous solutions was
poured into the solution, and then the mixture was extracted with
EtOAc three times (scheme 2, pic b). The supernatant was
combined and dried with Mg2SO4. Removing the solvent under
vacuum affords analytically pure product 5a in 97% yield
(scheme 2, pic c). This reaction clearly shows the potential in
practical organic synthesis since because of its green and mild
reaction conditions as well as the simple process operation.
4.2 Typical procedure for preparation of targeted molecules
Under argon, alkenes or alkynes, I2 and H3PO3 were added
into a 10 mL dried Schlenk tube equipped with a magnetic stir
bar, then solvent was charged. The tube was stirred at indicated
temperature and time. After reaction, the mixture was quenched
by 5.0 wt% Na2S2O3 aqueous solution and was extracted with
EtOAc three times. Then the combined the organic layer was
dried over Mg2SO4 and filtrated. The filtrate was concentrated
and the residue was further purified by column chromatography
on silica gel (or GPC) to give the product.
Under air, ethynylbenzene 3 and I2 were added into a 10 mL
dried Schlenk tube equipped with a magnetic stir bar, then 1.0
mL H2O was charged. The tube was stirred at room temperature
for indicated time. After reaction, the mixture was quenched by
5.0 wt % Na2S2O3 aqueous solution and was extracted with
EtOAc three times. Then the combined the organic layer was
dried over Mg2SO4 and filtrated. After evaporation of the solvent
under reduced pressure, the analytically pure product was
obtained.
Although the detailed mechanism was not clear, a plausible
reaction path has been depicted based on literatures. As shown in
scheme 3, H3PO3 may react with I2 to form HI that then, follows
the Markovnikov rule, adds to alkenes or alkyne leads to the
corresponding organoiodides (eq. 1). For the double-iodination of
alkynes, it is assumed that molecule iodine undergoes electronic
anti-addition to alkynes via a cyclic iodonium ion to afford the
1,2-diioalkens (eq. 2).20,21
4.2.1 (1-Iodoethyl)benzene (2a)3
1
Colorless oil, yield 90%; H NMR (400 MHz CDCl3): δ 7.45–
7.42 (m, 2H), 7.32–7.22 (m, 3H), 5.40 (q, J = 7.1 Hz, 1H), 2.21
(d, J = 7.2 Hz, 3H). 13C NMR (100 MHz CDCl3): δ 145.45,
128.78, 128.02, 126.63, 29.05, 26.21. GC-MS (EI, 70 eV) m/z =
232 (M+).
4.2.2 1-(1-Iodoethyl)-4-methylbenzene (2b)18
Light brown oil, yield 71%; 1H NMR (400 MHz CDCl3): δ 7.24–
7.23 (m, 2H), 7.01–6.99 (m, 2H), 5.31 (q, J = 7.0 Hz, 1H), 2.20
(s, 3H), 2.09 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz CDCl3): δ
142.54, 137.86, 129.42, 126.47, 29.09, 26.87, 21.29. GC-MS (EI,
70 eV) m/z = 246 (M+).
Scheme 3. A possible mechanism.
4.2.3 1-Fluoro-4-(1-iodoethyl)benzene (2c)3
3. Conclusion
1
Colorless oil, yield 75%; H NMR (400 MHz CDCl3): δ 7.46–
7.43 (m, 2H), 7.04–7.00 (m, 2H), 5.42 (q, J = 7.0 Hz, 1H), 2.23
(d, J = 7.0 Hz, 3H). 13C NMR (100 MHz CDCl3): δ 161.94 (d, J =
246 Hz), 141.34 (d, J = 3.4 Hz), 128.28 (d, J = 8.1 Hz), 115.60 (d,
J = 21.5 Hz), 29.19, 24.97. GC-MS (EI, 70 eV) m/z = 250 (M+).
In summary, we have successfully demonstrated the double-
iodination of terminal alkynes using iodine under mild conditions.
This approach has advantages such as using H2O as solvent, easy
scale-up and simple work-up. What’s more, by using the
combination of iodine and the cheap and low-toxic hydrogen
source H3PO3, for the first time, the selective hydroiodination of
various alkynes and alkenes, were achieved, that selectively
generate the corresponding Markovnikov-type products in good
yields. This reaction provided a simple and practical protocol to
synthesize a wide range of alkyl and alkenyl iodides, which are
important building blocks in organic synthesis.
4.2.4 1-Chloro-4-(1-iodoethyl)benzene (2d)3
Light brown oil, yield 84%; 1H NMR (400 MHz CDCl3): δ 7.39–
7.36 (m, 2H), 7.28–7.24 (m, 2H), 5.35 (t, J = 7.2 Hz, 1H), 2.18 (d,
J = 7.1 Hz, 3H). 13C NMR (100 MHz CDCl3): δ 144.03, 133.51,
128.95, 127.99, 28.97, 24.45. GC-MS (EI, 70 eV) m/z = 266
(M+).
4.2.5 1-Bromo-4-(1-iodoethyl)benzene (2e)3
4. Experimental section
White solid, yield 72%; 1H NMR (400 MHz CDCl3): δ 7.36–7.33
(m, 2H), 7.25–7.22 (m, 2H), 5.26 (t, J = 7.0 Hz, 1H), 2.11 (d, J =
7.5 Hz, 3H). 13C NMR (100 MHz CDCl3): δ 144.46, 131.84,
128.22, 121.56, 28.80, 24.31. GC-MS (EI, 70 eV) m/z = 311
(M+).
4.1 General information
Unless otherwise noted, all reactions were carried out in oven-
dried Schlenk tubes under argon. Reagents and solvents were
obtained from TCI or Wako Pure Chemical Industries, Ltd, and
purified according to standard methods. Flash column
chromatography was performed using 200-300 mesh silica gel.
Visualization on TLC was achieved by the use of UV light (254
nm). Shimadzu GC-2010 equipped with FID detector was used to
analysis the reaction mixture. 1H NMR and 13C NMR
4.2.6 1-(1-Iodoethyl)-4-(trifluoromethyl)benzene (2f)
1
Colorless oil, yield 91%; H NMR (400 MHz CDCl3): δ 7.57–
7.52 (m, 4H), 5.36 (q, J = 7.1 Hz, 1H), 2.21 (d, J = 7.2 Hz, 3H).

5
13C NMR (100 MHz CDCl3): δ 149.27, 130.48 (q, J = 32 Hz),
4.2.16 1-(1-Iodovinyl)naphthalene (4g)20
ACCEPTED MANUSCRIPT
127.02, 125.81 (q, J = 36 Hz), 124.01 (q, J = 271 Hz), 28.62,
Light yellow oil, yield 87%; 1H NMR (400 MHz CDCl3): δ 8.23–
8.20 (m, 1H), 7.90–7.82 (m, 2H), 7.63–7.58 (m, 1H), 7.54–7.48
(m, 2H), 7.44–7.40 (m, 1H), 6.38 (d, J = 1.1 Hz, 1H), 6.34 (d, J =
1.0 Hz, 1H). 13C NMR (100 MHz CDCl3): δ 141.63, 133.78,
131.23, 129.88, 128.98, 128.33, 126.40, 126.24, 125.82, 125.43,
125.26, 102.42. GC-MS (EI, 70 eV) m/z = 280 (M+).
23.21. GC-MS (EI, 70 eV) m/z = 300 (M+).
4.2.7 2-Iodooctane (2g)3
1
Colorless oil, yield 94%; H NMR (400 MHz CDCl3): δ 4.22–
4.14 (m, 1H), 1.91–1.50 (d, J = 6.8 Hz, 3H), 1.84–1.79 (m, 1H),
1.64–1.55 (m, 1H), 1.38–1.28 (m, 8H), 0.89–0.86 (m, 3H). 13C
NMR (100 MHz CDCl3): δ 43.03, 31.76, 30.96, 29.76, 29.02,
28.51, 22.68, 14.15. GC-MS (EI, 70 eV) m/z = 240 (M+).
4.2.17 (E)-(1-Iodoethene-1,2-diyl)dibenzene (4h)1f
Brown oil, yield 89%; 1H NMR (400 MHz CDCl3): δ 7.46 (s, 1H),
7.37–7.28 (m, 5H), 7.16–7.11 (m, 3H), 6.97–6.94 (m, 2H). 13C
NMR (100 MHz CDCl3): δ 143.11, 141.45, 137.28, 128.87,
128.82, 128.52, 128.28, 127.67, 98.57. GC-MS (EI, 70 eV) m/z =
306 (M+).
4.2.8 4-Iodooctane (2h)3
1
Colorless oil, yield 93%; H NMR (400 MHz CDCl3): δ 4.15–
4.09 (m, 1H), 1.90–1.80 (m, 2H), 1.72–1.29 (m, 8H), 0.93–0.89
(m, 6H). 13C NMR (100 MHz CDCl3): δ 42.82, 40.51, 40.36,
31.77, 22.88, 22.07, 14.08, 13.36. GC-MS (EI, 70 eV) m/z = 204
(M+).
4.2.18 (Z)-4-Iodooct-4-ene (4i)11b
Colorless oil, yield 89%; 1H NMR (400 MHz CDCl3): δ 5.46 (t, J
= 8.0 Hz, 1H), 2.42 (t, J = 7.2 Hz, 2H), 2.08 (m, 2H), 1.56–1.39
(m, 4H), 0.94–0.85 (m, 6H). 13C NMR (100 MHz CDCl3): δ
134.87, 109.70, 47.19, 38.44, 22.57, 21.81, 13.79, 12.71. GC-MS
(EI, 70 eV) m/z = 238 (M+).
4.2.9 Iodocyclooctane (2i )3
1
Colorless oil, yield 65%; H NMR (400 MHz CDCl3): δ 4.62–
4.55 (m, 1H), 2.25–2.19 (m, 4H), 1.69–1.41 (m, 10H). 13C NMR
(100 MHz CDCl3): δ 38.40, 38.02, 27.53, 26.74, 25.23. GC-MS
(EI, 70 eV) m/z = 238 (M+).
4.2.19 (E)-(1,2-Diiodovinyl)benzene (5a)13b
1
4.2.10 (1-Iodovinyl)benzene (4a)11a
Light yellow solid, yield 98%; H NMR (400 MHz CDCl3): δ
7.37–7.34 (m, 5H), 7.26 (s, 1H). 13C NMR (100 MHz CDCl3): δ
143.18, 129.07, 128.60, 128.53, 96.28, 80.92. GC-MS (EI, 70 eV)
m/z = 356 (M+).
4.2.20 (E)-1-(1,2-Diiodovinyl)-4-methylbenzene (5b)23
Light yellow oil, yield 92%; 1H NMR (400 MHz CDCl3): δ 7.29–
7.25 (m, 2H), 7.22 (s, 1H), 7.18–7.16 (m, 2H), 2.36 (s, 3H). 13C
NMR (100 MHz CDCl3): δ 140.26, 139.18, 129.19, 128.58,
96.73, 80.35, 21.57. GC-MS (EI, 70 eV) m/z = 370 (M+).
1
Colorless oil, yield 85%; H NMR (400 MHz CDCl3): δ 7.53–
7.49 (m, 2H), 7.33–7.27 (m, 3H), 6.47 (d, J = 1.8 Hz, 1H), 6.08
(d, J = 1.8 Hz, 1H). 13C NMR (100 MHz CDCl3): δ 141.77,
128.95, 128.33, 128.17, 127.39, 107.52. GC-MS (EI, 70 eV) m/z
= 230 (M+).
4.2.11 1-(1-Iodovinyl)-4-methylbenzene (4b)19
1
Colorless oil, yield 79%; H NMR (400 MHz CDCl3): δ 7.43–
7.40 (m, 2H), 7.11 (d, d, J = 8.0 Hz, 2H), 6.43 (d, J = 1.7 Hz, 1H),
6.04 (d, J = 1.7 Hz, 1H), 2.36 (s, 3H). 13C NMR (100 MHz
CDCl3): δ 139.02, 128.97, 128.09, 126.56, 107.78, 21.22. GC-
MS (EI, 70 eV) m/z = 244 (M+).
4.2.21 (E)-1-(Tert-butyl)-4-(1,2-diiodovinyl)benzene (5c)21
Light yellow oil, yield 97%; 1H NMR (400 MHz CDCl3): δ 7.38–
7.31 (m, 4H), 7.23 (s, 1H), 1.34 (s, 9H). 13C NMR (100 MHz
CDCl3): δ 152.20, 139.89, 128.51, 125.39, 96.96, 80.04, 34.93,
31.36. GC-MS (EI, 70 eV) m/z = 412 (M+).
4.2.12 1-(Tert-butyl)-4-(1-iodovinyl)benzene (4c)19
1
Colorless oil, yield 75%; H NMR (400 MHz CDCl3): δ 7.49–
7.45 (m, 2H), 7.35–7.32 (m, 2H), 6.45 (d, J = 1.6 Hz, 1H), 6.04
(d, J = 1.7 Hz, 1H), 1.32 (m, 9H). 13C NMR (100 MHz CDCl3): δ
152.19, 138.85, 127.92, 126.60, 125.25, 107.72, 34.72, 31.33.
GC-MS (EI, 70 eV) m/z = 286 (M+).
4.2.22 (E)-1-(1,2-Diiodovinyl)-4-methoxybenzene (5d)13b
Light yellow oil, yield 95%; 1H NMR (400 MHz CDCl3): δ 7.35–
7.32 (m, 2H), 7.19 (s, 1H), 6.89–6.85 (m, 2H), 3.82 (s, 3H). 13C
NMR (100 MHz CDCl3): δ 159.89, 135.33, 130.36, 113.78,
96.77, 80.06, 55.48. GC-MS (EI, 70 eV) m/z = 386 (M+).
4.2.13 1-Chloro-2-(1-iodovinyl)benzene (4d)
1
Colorless oil, yield 55%; H NMR (400 MHz CDCl3): δ 7.36–
4.2.23 (E)-1-Chloro-4-(1,2-diiodovinyl)benzene (5e)22
White solid, yield 99%; 1H NMR (400 MHz CDCl3): δ 7.35–7.28
(m, 5H). 13C NMR (100 MHz CDCl3): δ 141.59, 134.93, 130.04,
128.83, 94.62, 81.73. GC-MS (EI, 70 eV) m/z = 390 (M+).
7.28 (m, 2H), 7.25–7.21 (m, 2H), 6.23–6.21 (m, 2H). 13C NMR
(100 MHz CDCl3): δ 142.21, 131.91, 131.52, 130.07, 130.04,
129.72, 126.81, 99.92. GC-MS (EI, 70 eV) m/z = 264 (M+).
4.2.14 1-Fluoro-4-(1-iodovinyl)benzene (4e)1g
4.2.24 (E)-1-(1,2-Diiodovinyl)-4-(trifluoromethyl)benzene (5f)21
1
Colorless oil, yield 80%; H NMR (400 MHz CDCl3): δ 7.51–
Light yellow oil, yield 98%; 1H NMR (400 MHz CDCl3): δ 7.65–
7.63 (d, J = 8.0 Hz, 2H), 7.48–7.46 (d, J = 8.0 Hz, 2H), 7.36 (s,
1H). 13C NMR (100 MHz CDCl3): δ 146.66, 130.89 (q, J = 32
Hz), 129.06, 125.68 (q, J = 3.0 Hz), 123.86 (q, J = 271 Hz),
93.88, 82.58. GC-MS (EI, 70 eV) m/z = 424 (M+).
7.46 (m, 2H), 7.02–6.96 (m, 2H), 6.39 (d, J = 1.8 Hz, 1H), 6.05
(d, J = 1.8 Hz, 1H). 13C NMR (100 MHz CDCl3): δ 162.98 (d, J =
247 Hz), 138.02 (d, J = 3.0 Hz), 129.88 (d, J = 8.0 Hz), 127.46,
115.14 (d, J = 22 Hz), 105.79. GC-MS (EI, 70 eV) m/z = 248
(M+).
4.2.25 (E)-4-(1,2-Diiodovinyl)benzaldehyde (5g)
4.2.15 1-(1-Iodovinyl)-4-(trifluoromethyl)benzene (4f)11a
Light yellow oil, yield 99%; 1H NMR (400 MHz CDCl3): δ 10.02
(s, 1H), 7.89–7.86 (m, 2H), 7.50–7.48 (m, 2H), 7.35 (s, 1H). 13C
NMR (100 MHz CDCl3): δ 191.40, 148.92, 136.25, 129.94,
129.30, 93.97, 82.52. GC-MS (EI, 70 eV) m/z = 384 (M+).
1
Colorless oil, yield 56%; H NMR (400 MHz CDCl3): δ 7.62–
7.55 (m, 4H), 6.53 (d, J = 1.7 Hz, 1H), 6.18 (d, J = 1.7 Hz, 1H).
13C NMR (100 MHz CDCl3): δ 145.16, 130.98 (q, J = 148 Hz),
129.31, 128.46, 126.78, 125.34 (q, J = 14 Hz), 104.98. GC-MS
(EI, 70 eV) m/z = 298 (M+).
4.2.26 (E)-1-(4-(1,2-Diiodovinyl)phenyl)ethanone (5h)

6
Tetrahedron
1
Light yellow oil, yield 98%; H NMR (400 MHz CDCl3): δ
[10] Bartoli, G.; Cipolletti, R.; Antonio, G. D.; Giovannini, R.;
Lanari, S.; Marcolini, M.; Marcantoni, E. Org. Biomol. Chem.
2010, 8, 3509–3517.
ACCEPTED MANUSCRIPT
7.95–7.92 (m, 2H), 7.43–7.40 (m, 2H), 7.32 (s, 1H), 2.59 (s, 3H).
13C NMR (100 MHz CDCl3): δ 197.24, 147.60, 137.08, 128.91,
128.62, 94.44, 82.27, 26.84. GC-MS (EI, 70 eV) m/z = 398 (M+).
4.2.27 (E)-1-(1,2-Diiodovinyl)naphthalene (5i)23
[11] (a) Kawaguchi, S.-i.; Ogawa, A. Org. Lett. 2010, 12, 1893–
1895. (b) Kawaguchi, S.-i.; Masuno, H.; Sonoda, M.; Nomoto, A.;
Ogawa, A. Tetrahedron, 2012, 68, 9818–9825. (c) Kawaguchi,
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6779−6783.
1
Light yellow solid, yield 99%; H NMR (400 MHz CDCl3): δ
7.94–7.87 (m, 3H), 7.63–7.58 (m, 1H), 7.55–7.40 (m, 4H). 13C
NMR (100 MHz CDCl3): δ 141.01, 133.91, 129.38, 128.62,
126.69, 125.76, 125.65, 125.14, 94.38, 84.53. GC-MS (EI, 70 eV)
m/z = 406 (M+).
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4.2.28 (E)-1,2-Diiodooct-1-ene (5j)21
1
Colorless oil, yield 95%; H NMR (400 MHz CDCl3): δ 6.79 (s,
[13] (a) Rao, D. S.; Reddy, T. R. Kashyap, S. Org. Biomol. Chem.
2018, 16, 1508-1518; (d) Liu, Y.; Huang, D.; Huang, J.; Maruoka,
K. J. Org. Chem. 2017, 82, 11865−11871.
1H), 2.49 (t, J = 8.0 Hz, 2H), 1.55–1.49 (m, 2H), 1.35–1.31 (m,
6H), 0.91–0.88 (m, 3H). 13C NMR (100 MHz CDCl3): δ 104.56,
78.99, 44.77, 31.70, 28.23, 27.95, 22.64, 14.17. GC-MS (EI, 70
eV) m/z = 364 (M+).
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Acknowledgments
JX thanks a postdoc fellowship from AIST and partial support
from HNNSF (2017JJ3081).
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ACCEPTED MANUSCRIPT
ꢀ
For the first time, using I2/ H3PO3 system, alkenes and alkynes were hydroiodinated
successfully in high selectivity.
ꢀ
ꢀ
In the presence of I2, alkynes could be double-iodinated under green and mild conditions.
A green and practical protocol and the work-up procedure is simple.