Regio- and stereoselective co-iodination of olefins using NH4I and Oxone

Article abstract of DOI:10.1080/00397911.2016.1188960

A simple, efficient, and environmentally benign protocol for the synthesis of vicinal iodohydrins and iodoesters from olefins using NH₄I and Oxone in CH₃CN/H₂O (1:1) and dimethylformamide (DMF) / dimethylacetamide (DMA), respectively, without employing a catalyst at room temperature is described. Regio- and stereoselective iodohydroxylation and iodoesterification of various olefins with anti fashion, following Markonikov’s rule, was achieved and the corresponding products were obtained in good to excellent yields. In addition, 1,2-disubstituted olefins afforded excellent diastereoselectivity.

Full text of DOI:10.1080/00397911.2016.1188960

Synthetic Communications
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Regio- and Stereoselective Co-Iodination of Olefins
Using NH4I and Oxone®
Chevella Durgaiah, Mameda Naresh, Macharla Arun Kumar, Peraka Swamy,
Marri Mahender Reddy, Kodumuri Srujana & Nama Narender
To cite this article: Chevella Durgaiah, Mameda Naresh, Macharla Arun Kumar, Peraka
Swamy, Marri Mahender Reddy, Kodumuri Srujana & Nama Narender (2016): Regio- and
Stereoselective Co-Iodination of Olefins Using NH4I and Oxone®, Synthetic Communications,
DOI: 10.1080/00397911.2016.1188960
To link to this article: http://dx.doi.org/10.1080/00397911.2016.1188960
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Date: 26 May 2016, At: 10:30

Regio- and Stereoselective Co-Iodination of Olefins using NH4I and Oxone®
Chevella Durgaiah1, Mameda Naresh1,2, Macharla Arun Kumar1, Peraka Swamy1,2, Marri
Mahender Reddy1, Kodumuri Srujana1, Nama Narender1,2
1I&PC Division, CSIR-Indian Institute of Chemical Technology, Hyderabad,
Telangana, India 2Academy of Scientific and Innovative Research, CSIR-IICT,
Hyderabad, Telangana, India
Corresponding author Nama Narender I&PC Division, CSIR-Indian Institute of
Chemical Technology, Hyderabad-500007, Telangana, India E-mail:
narendern33@yahoo.co.in; nama@iict.res.in
ABSTRACT
A simple, efficient and environmentally benign protocol for the synthesis of vicinal
iodohydrins and iodoesters from olefins using NH4I and oxone® in CH3CN:H2O (1:1) and
DMF/DMA, respectively, without employing a catalyst at room temperature is described.
Regio- and stereo selective iodohydroxylation and iodoesterification of various olefins
with anti fashion, following Markonikov’s rule was achieved and the corresponding
products were obtained in good to excellent yields. In addition, 1,2-disubstituted olefins
afforded excellent diastereoselectivity.
GRAPHICAL ABSTRACT
KEYWORDS: Co-Iodination; Diastereoselectivity; NH4I; Olefins; Oxone®
1

INTRODUCTION
Vicinal functionalization of olefins is a remarkable fundamental process in organic
synthesis, especially when the reaction affords products in regio- and stereoselective
manner. In particular, simultaneous installation of two different functional groups, such
as hydroxy or ester and halogen, have attracted much attention in synthetic organic
chemistry.[1] Vicinal halohydrin derivatives have extensive applications in modern
organic synthesis and they serve as highly adaptable building blocks,[2] valuable bioactive
materials[3] and key intermediates.[4] Production of halohydrins from alkenes is a well-
known procedure.[5] Iodohydrines cannot be prepared by the direct reaction of olefins
with water solutions of the iodine, in contrast with their homologous chloro- and
bromohydrins, because reversibility of the addition of hypoiodous acid to the double
bond. Indeed, in most cases, an iodide ion scavenger[6] is generally needed to obtain
satisfactory yields.
Some other protocols include the use of H5IO6/NaHSO3,[7] N-iodoimides,[8] N-
iodosaccharin,[9] bis(pyridine)iodine(I)salts,[10] DMDO/MeI,[11] triodide ion,[12] K10-
MX/I2/MWI,[13] IBX-I2[14] and I2/H2O/clays[15] for the vicinal iodohydroxylation of
alkenes have also been reported. Alternatively, iodohydrins are accessible from epoxides
using different reagents, such as hydroiodicacid,[16] I2/crown ethers,[17] Ti(O-i-Pr)4/I2
complex,[18] metal iodides[19] or ionic liquid.[20] Iodohydrins could also be synthesized
from carbonyl compounds with CH2I2 (iodomethylation) in the presence of SmI2[21] or
halogen exchange reaction[22] of other halohydrins. However, most of the current methods
usually have disadvantages of using expensive and toxic reagents, tedious work-up
2

procedures, producing low yields and limited applicability to olefinic substrates. Due to
the limitations of the above mentioned approaches and the wide spread attention in iodine
containing compounds, there is a need for the development of an efficient and sustainable
method for the production of iodohydrins and iodoesters.
Oxone® (2KHSO5.KHSO4.K2SO4), a potassium triple salt containing potassium
peroxymonosulfate, is a white crystalline solid, easy to handle, soluble in water and
yields non-polluting byproducts. Because of the discovery of multiple innovative
applications, oxone® has become an increasingly popular reagent for several organic
transformations.[23] In continuation of our efforts toward the development of novel and
eco-friendly halogenation protocols,[24],[25],[26] herein we report a facile method for the
synthesis of β-iodohydrins and β-iodoesters from olefins using NH4I as a iodine source
and oxone® as an oxidant under mild conditions in CH3CN:H2O (1:1) and DMF/DMA,
respectively, without employing a catalyst (Scheme 1).
RESULTS AND DISCUSSION
Initially, we investigated the iodohydroxylation of styrene with NH4I and oxone® in
various non-polar and polar solvents (single or their combination with water) and the
results are described in Table 1. The results revealed that the water combination with
polar solvents significantly improved the yield of corresponding iodohydrin (Table 1,
entries 13-17). Remarkably, the best results were obtained when a mixture of CH3CN and
water was (1:1) used as a solvent system among others in terms of reaction yield and time
(Table 1, entry 13).
3

With the optimal conditions in hand, the scope and limitations of the method were
explored (Scheme 1) with a variety of alkenes (terminal and internal alkenes) and the
results are presented in Table 2. First, we examined the aromatic substrates with a
terminal double bond and obtained the corresponding products 1a–j in good to excellent
yields with exclusive Markovnikov regioselectivity (Table 2). Aromatic terminal alkenes
with activated phenyl ring including 4-methoxystyrene (1b), 4-methylstyrene (1c) and
2,4-dimethylstyrene (1d) furnished the respective products 2b, 2c and 2d in 72%, 95%
and 91% yields, respectively (Table 2, entries 2-4). Whereas, in the case of 3-
nitrostyrene (1g), longer reaction time (60 min) was required compared to activated
aromatic alkenes to give the corresponding product (2g) in good yield (78%) (Table 2,
entry 7). Halo substituted styrenes such as 4-chlorostyrene (1e) and 4-bromostyrene (1f)
generated the corresponding iodohydroxylation products 2e and 2f in excellent yields due
to the inductive and resonance effect of halogen (Cl, Br) groups (Table 2, entries 5 and
6). Unfortunately, 2-vinylpyridine (1h) failed to react even for prolonged reaction time
(24 h) and recovered in quantitative yield (Table 2, entry 8). Polyaromatic alkene, i.e. 2-
vinylnaphthalene (1i) also reacted well and afforded the respective product 2i in 80%
yield (Table 2, entry 9). In addition, the α-substituted styrene derivative (1j) provided the
corresponding product (2j) in 97% yield (Table 2, entry 10) under similar conditions.
Subsequently, 1,2-disubstituted unsymmetrical and symmetrical olefins were submitted
to the vicinal iodohydroxylation and produced the corresponding products 2k-2o in good
to excellent yields with excellent diastereoselectivity (Table 2). In all cases, complete
4

regio- and predominant trans-diastereoselective addition was observed. Unsymmetrical
trans-alkenes 1k and 1l selectively formed the corresponding erythro isomers 2k and 2l
in 84% and 75% yields, respectively (Table 2, entries 11 and 12). Symmetrical and
unsymmetrical cyclic olefins, such as indene (1m), 1,2-dihydronaphthalene (1n) and
cyclohexene (1o) reacted smoothly and yielded the corresponding products 2m, 2n and
2o in 95%, 92% and 93% yields, respectively (Table 2, entries 13-15). In case of
monosubstituted linear olefin, a limited anti-Markovnikov product was also observed.
For example, 1-octene (1p) gave the corresponding Markovnikov’s product (2p) (76%)
as well as anti-Markovnikov’s product (2p1) (23%) (Table 2, entry 16). Mixed
regioselectivity was observed with linear asymmetric trans-alkene, i.e., trans-2-octene
(1q) furnished the erythro-2-iodo-3-octanol (2q) and erythro-3-iodo-2-octanol (2q1) in
the ratio of 32:62 (Table 2, entry 17).
Interestingly, when DMF or DMA was used as a reaction medium under similar
reaction conditions, the iodoester product was obtained instead of the expected
iodohydrin (Table 1, entries 18 and 19). Stimulated by these affirmative
preliminary results, subsequently, we considered to develop a methodology for the
iodoesterification of alkenes. Only a few methods have been reported for the preparation
of iodoesters directly from olefins such as KIO3
oxide [28]
,
[27] tetrafluoroboricacid/I2/copper(II)
[31]
,
dichloroiodoisocyanuric acid/Ac2O,[29] Fe2(SO4)3/I2,[30] Ce(OTf)4/I2
NH4I/H2O2/Ac2O.[32] To improve the yield of iodoformate (3a), styrene (1 mmol) was
allowed to react with different mole ratios of oxone® (1.0, 1.1) in the presence of NH4I
(1.1) in DMF (10 mL) (Table 1, entries 20 and 21). The results revealed that a 1 : 1.1 :
5

1.1 mole ratio of styrene, oxone® and NH4I at room temperature was the optimum
reaction conditions for iodoformyloxylation of olefins.
Under the optimized conditions, we successfully carried out the iodoformyloxylation of
various olefins by using DMF as a nucleophilic solvent and obtained the corresponding
β-iodoformate derivatives in good to excellent yields (Table 3). Olefins having either
activated (1b-c) or inactivated arenes (1d-f) reacted well and furnished the respective
vicinal iodoformate products 3b-f in 70-94% yields. Heteroaromatic olefin (1g) and 2-
vinylnaphthalene (1h) also provided the corresponding products 3g and 3h in 90% and
82% yields, respectively (Table 3, entries 7 and 8). The use of 1,2-disubstituted
symmetrical and unsymmetrical olefins generated the corresponding vicinal
iodoformyloxylation products 3i-3k with high regio- and excellent diastereoselectivities
(Table 3). The activated olefinic substrates 1i and 1j selectively yielded the
corresponding erythro isomer products 3i and 3j in 79% and 92% yields, respectively
(Table 3, entries 9-10). Similarly, cyclic olefin (1k) afforded the respective vicinal
iodoformate product 3k in 94% yield (Table 3, entry 11). Linear aliphatic olefins (1l and
1m) gave the corresponding Markovnikov’s products (3l and 3m) as well as anti-
Markovnikov products (3l1 and 3m1) (Table 3, entries 12 and 13). However, erythro
isomer products were exclusively obtained for trans-2-octene (1m) (Table 3, entry 13).
Inspired by the above results obtained for the iodoformyloxylation of olefins in DMF as a
nucleophilic solvent under mild conditions, we then turned our attention to further
investigate the iodoacetoxylation of olefins in an another nucleophilic solvent i.e. DMA.
6

Unfortunately, activated aromatic olefins provided the corresponding iodohydrin
derivatives instead of iodoacetates (Table 4, entries 2-4), whereas inactivated aromatic
olefins reacted well and furnished the respective iodoacetate products in good to excellent
yields (Table 4, entries 5-8).
A probable mechanistic pathway for the formation of iodohydrins and iodoesters from
olefins is depicted in Scheme 2. It is assumed that oxone efficiently oxidizes the I-
(NH4I) to I+ (HO-I+), which further reacts (electrophilic addition) with olefin I to give a
three membered cyclic iodonium ion intermediate II. The cyclic intermediate II
undergoes ring opening by the oxygen of DMF or DMA via SN2 pathway to produce an
iminium ion III intermediate, which upon hydrolysis gave the vicinal iodoester product
IV. In case of iodohydrin formation, intermediate II reacts with the nucleophile (OH-) in
same manner to afford the corresponding α-hydroxy β-iodo derivative (V).
In all aromatic olefins, for both the vicinal iodohydroxylation and iodoesterification, the
incoming nucleophile attacks at the benzylic position of cyclic intermediate exclusively.
The regioselectivity of aromatic olefins can be explained by considering the fact that the
α-position (benzylic) is more positive than the β-position because of the presence of the
aromatic ring. Nucleophilic ring opening of the cyclic iodonium intermediate presumably
takes place from the more positive α-position. Furthermore, most of the 1,2-disubstituted
alkenes exhibited predominant anti stereoselectivity. The stereochemistry of the products
was confirmed by analysis of the 1H NMR data.
7

CONCLUSIONS
In conclusion, we have demonstrated a novel and highly efficient approach for the regio-
and stereoselective iodohydroxylation and iodoesterification of olefins using NH4I-
oxone reagent system. This method is applicable to different kinds of olefins, such as
terminal, 1,2-disubstituted unsymmetrical and symmetrical olefins. The present protocol
offers several advantages including commercial availability of the reagents, high yields,
mild reaction conditions, high atom economy (100% with respect to iodine), no evolution
of hydrogen iodide, high regio- and stereo selectivity of the reactions, economical process
with easier setup/work-up procedures and environmental friendly. Hence it offers useful
alternative to the existing methods.
EXPERIMENTAL SECTION
All chemicals used were reagent grade and used as received without further
purification. 1H NMR spectra were recorded at 300, 400 and 500 MHz and 13C
NMR spectra 75 MHz in CDCl3 or DMSO-D6. The chemical shifts (δ) are reported
in ppm units relative to TMS as an internal standard for 1H NMR and CDCl3 for
13C NMR spectra. Coupling constants (J) are reported in hertz (Hz) and
multiplicities are indicated as follows: s (singlet), bs (broad singlet), d (doublet),
dd (doublet of doublet), t (triplet), m (multiplet). Column chromatography was
carried out using silica gel (100-200 mesh).
General Procedure For Vicinal Iodohydroxylation Of Olefins
8

Oxone (0.461 g, 0.75 mmol) was slowly added to a well stirred solution of NH4I
(0.160 g, 1.1 mmol) and olefin (1 mmol) in CH3CN:H2O (1:1) (10 mL) and the
reaction mixture was allowed to stir at room temperature for the time shown in
Table 2. When the reaction completion (TLC) or an appropriate time, the mixture
was filtered and the solvent was evaporated under reduced pressure. The residue
was dissolved in EtOAc (25 mL) and the solution was filtered and washed
successively with 0.2 M aq Na2S2O3 and H2O. The organic layer was dried
(Na2SO4) and concentrated in vacuo. The crude product was purified by column
chromatography (silica gel, 5–50% EtOAc-hexane) to give pure products. All the
products were identified on the basis of 1H NMR, 13C NMR and Mass
spectroscopy.
General Procedure For Vicinal Iodoesterification Of Olefins
An olefin was slowly added to a well stirred (30 min) solution of NH4I (0.160 g, 1.1
mmol) and oxone (0.676 g, 1.1 mmol) in DMF/DMA (10 mL) and the reaction mixture
was stirred at room temperature until the olefin completely disappeared (monitored by
TLC) or an appropriate time, quenched with ice water and extracted with Et2O (2 x 15
mL). Than the combined organic layers were washed with 0.2 M aq Na2S2O3 and H2O,
dried (Na2SO4) and concentrated in vacuo. The resulting crude residue was purified by
column chromatography (silica gel, 5-50% EtOAc-hexane) to give pure products. All the
products were identified on the basis of 1H NMR, 13C NMR and Mass spectroscopy.
SUPPLEMENTARY MATERIAL
9

Experimental details and 1H and 13C NMR spectral data for this article can be accessed
on the publisher’s website.
ACKNOWLEDGEMENTS
We thank the CSIR Network project CSC-0125 for financial support. Ch.D., M.N. and
M.M.R. acknowledge the financial support from CSIR, India in the form of fellowships.
P.S. and K.S. acknowledge the financial support from UGC, India in the form of
fellowship.
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13

Table 1. Iodohydroxylation of styrene-effect of solventa
S. No. Solvent
Time (h) Yieldb (%)
1
DCM
24
8
2
CHCl3
24
00
00
78
25
28
00
8
3
CCl4
24
4
CH3CN
24
5
Acetone
24
6
THF
24
7
DME
24
8
1,4-Dioxane
H2O
24
9
24
80
15
10
20
99
60
78
30
40
00 (48)c
10
11
12
13
14
15
16
17
18
DCM-H2O (1:1)
CHCl3-H2O(1:1)
CCl4-H2O (1:1)
CH3CN-H2O (1:1)
AcetoneH2O(1:1)
THF/H2O (1:1)
DME/H2O (1:1)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
1,4-Dioxane/H2O (1:1) 0.1
DMF
4
14

19
20
21
DMA
DMF
DMF
4
4
4
00 (45) d
00 (85)e
00 (96)f
a Reaction conditions: substrate 1a (1 mmol), NH4I (0.160 g, 1.1 mmol,), oxone®
(0.461 g, 0.75 mmol,), solvent (10 mL), room temperature.
b Isolated yields.
c Iodoformate product.
d Iodoacetate product.
e Oxone® (0.614 g, 1 mmol).
f Oxone® (0.676 g, 1.1mmol).
15

a
Table 2. Synthesis of β-iodohydrins from olefins using NH4I and oxone
Entry
1
Time (min) Product
10
Yieldb (%)
99
Olefin
1a
2a
2
1
72
1b
2b
3
4
5
8
95
91
90
1c
1d
1e
2c
5
2d
15
2e
6
7
8
15
60
24c
75
78
00
1f
2f
1g
1h
2g
2h
16

9
10
6
80
7
1i
1j
2i
10
2j
11
12
5
84
75
1k
1l
2k
10
2l
13
14
5
5
95
92
1m
1n
2m
2n
15
16
2
93
95
1o
1p
2o
15
2p (76%)
2p1 (23%)
17
15
94
1q
2q (32%)
2q1(62%)
a Reaction conditions: substrate 1a-q (1 mmol), NH4I (0.160 g, 1.1 mmol), oxone® (0.461
g, 0.75 mmol), CH3CN:H2O (1:1) (10 mL), room temperature.
17

b Isolated yields. c 24 h.
18

a
Table 3. Synthesis of iodoformates from olefins using NH4I and oxone
Entry Olefin Time (h) Product
Yieldb (%)
96
1
2
3
4
5
6
4
4
4
3
3
6
1a
1b
1c
1d
1e
1f
3a
70
75
94
93
83
3b
3c
3d
3e
3f
19

7
20
4
90
82
79
1g
1h
1i
3g
8
3h
9
4
3i
10
4
92
1j
3j
11
12
4
3
94
95
1k
1l
3k
3l (76%)
3l1 (23%)
13
3
94
1m
3m (55%)
3m1 (39%)
20

a Reaction conditions: substrate 1a-m (1 mmol), NH4I (0.160 g, 1.1 mmol), oxone®
(0.676 g, 1.1 mmol), DMF (10 mL), room temperature.
b Isolated yields.
21

a
Table 4. Synthesis of iodoacetates from olefins using NH4I and oxone
Entry Olefin Time (h) Product
Yieldb (%)
70
1
4
1a
4a
2
5
00 (91)c
1b
4b
3
4
5
6
3
2
6
7
00 (84)c
00 (91)c
70
1c
1d
1e
1f
4c
4d
4e
72
4f
22

7
8
6
76
88
1g
1h
4g
20
4h
a Reaction conditions: substrate 1a-h (1 mmol), NH4I (0.160 g, 1.1 mmol,), oxone®
(0.676 g, 1.1 mmol), DMA (10 mL), room temperature.
b Isolated yields. c Iodohydrin products.
23

Scheme 1. Vicinal functionalization of olefins using NH4I and oxone®.
24

Scheme 2. The plausible reaction mechanism.
25