Regioselective synthesis of α-iodoacetates from alkenes/ammonium acetate/I2 by Woodward's reaction

Article abstract of DOI:10.1081/SCC-200043180

Regioselective synthesis of α-iodoacetates from alkenes, ammonium acetate, and iodine in acetic acid is reported. The reaction is facile, fast, environmentally, friendly, and cost effective. α-Iodoacetates are obtained from both acyclic and cyclic alkenes

Full text of DOI:10.1081/SCC-200043180

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Regioselective Synthesis of
α‐Iodoacetates from Alkenes/
Ammonium Acetate/I by
2
Woodward's Reaction
a
b
Yi Yi Myint & M. A. Pasha
a
Department of Chemistry , Yadanabon
University , Myanmar
b
Department of Studies in Chemistry , Central
College Campus, Bangalore University , Bangalore,
560 001, India
Published online: 10 Jan 2011.
To cite this article: Yi Yi Myint & M. A. Pasha (2004) Regioselective Synthesis of
α‐Iodoacetates from Alkenes/Ammonium Acetate/I by Woodward's Reaction,
2
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 34:24, 4477-4482, DOI: 10.1081/SCC-200043180
To link to this article: http://dx.doi.org/10.1081/SCC-200043180
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SYNTHETIC COMMUNICATIONS
Vol. 34, No. 24, pp. 4477–4482, 2004
Regioselective Synthesis of a-Iodoacetates
from Alkenes/Ammonium Acetate/I by
Woodward’s Reaction
2
1
Yi Yi Myint and M. A. Pasha
2,*
1
Department of Chemistry, Yadanabon University, Myanmar
Department of Studies in Chemistry, Central College Campus,
Bangalore University, Bangalore, India
2
ABSTRACT
Regioselective synthesis of a-iodoacetates from alkenes, ammonium
acetate, and iodine in acetic acid is reported. The reaction is facile,
fast, environmentally, friendly, and cost effective. a-Iodoacetates are
obtained from both acyclic and cyclic alkenes in high yields ranging
from 80–95% within 10–20 min.
Key Words: a-Iodoacetates; Alkenes; Ammonium acetate; Molecular
iodine; Acetic acid.
*
Correspondence: M. A. Pasha, Department of Studies in Chemistry, Central College
Campus, Bangalore University, Bangalore 560 001, India; E-mail: m_af_pasha@
yahoo.co.in.
4
477
DOI: 10.1081/SCC-200043180
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

4
478
Myint and Pasha
a-Iodoacetates are important in organic synthesis as they can be trans-
formed into other functional groups such as cis- and trans-diols, monohydroxy
compounds, Grignard reagents, iodohydrins, diacetates, monoacetates,
hydroxy acetates, and epoxides. They are also used in C 22 C bond formation
reactions. There are only a few methods available in the literature for their
preparation. The reported methods require the use of heavy metal acetates
[
1–3]
[4]
[5,6]
[7]
like those of silver,
thallium(I), mercury(II),
Silver acetate is more commonly used for the iodoacetoxyla-
bismuth(III), or
[8–10]
copper(II).
tion of olefins with iodine in glacial acetic acid.
In this paper we report a novel and an extremely efficient addition reaction
of alkenes in the presence of iodine and ammonium acetate to give the corre-
sponding a-iodoacetates (Sch. 1). This reaction is environmentally benign
with no toxic by-products.
From Table 1, it is clear that different a-iodoacetates are obtained from
both acyclic and cyclic alkenes in excellent yields within very short reaction
periods (10–20 min). A noteworthy feature of the reaction is that it is selec-
tive, and the major product is a less-substituted iodo product (entries 7–11).
Cyclic alkenes furnish the trans-iodoacetates exclusively (entries 1–3).
In conclusion, a mild, highly efficient, convenient, selective, and environ-
mentally benign method for the preparation of a-iodoacetates in a short time
has been developed.
EXPERIMENTAL
Alkenes, ammonium acetate, and glacial acetic acid were obtained
from Spectrochem or Rankem. Nicolet 400D FT-IR spectrometer was
1
3
1
used for IR spectral analysis, C and HNMR spectra were recorded on a
00/400 MHz, respectively, using a Bruker instrument. Elemental analysis
was performed on ThermoFinnigan FLASH EA 1112 CHNS analyser.
1
Scheme 1.

Regioselective Synthesis of a-Iodoacetates
4479
Table 1. a-Iodoacetoxylation of olefins with ammonium acetate and iodine in
acetic acid.
a
Time Yield
(min)
Entry
1
Alkene
Product
(%)
10
94
2
3
15
12
94
90
4
5
6
15
15
15
82
80
93
7
8
9
10
15
15
15
20
95
90
91
87
93
1
1
0
1
a
Isolated by column chromatography.
The chemical shift values (d ppm) are reported relative to TMS in CDCl3
as solvent.
Preparation of Trans-1-Acetoxy-2-Iodocyclohexane:
General Procedure
Ammonium acetate (0.89 g, 5 mmol), glacial acetic acid (5 mL), and
cyclohexene (0.82 g, 10 mmol) were taken in a two-neck, 50-mL RB flask.

4
480
Myint and Pasha
Iodine (2.54 g, 10 mmol) in glacial acetic acid (5 mL) was added slowly to the
above mixture, which was stirred at 258C. The reaction was monitored by TLC
(
5% EtOAc: pentane). The reaction mixture was extracted with ether
3 Â 10 mL) and the combined ethereal extract was washed with saturated
(
NaHCO solution and water, and dried over anhydrous Na SO . The crude
product was subjected to silica gel chromatography to give trans-1-acetoxy-
3
2
4
2
1
-iodocyclohexane (2.52 g, 94%).
Trans-1-acetoxy-2-iodocyclohexane: 2.52g, 94%. IR (cm ): 1740, 1243,
21
1
036, 420. HNMR: d 2.06 (s, –COCH ), 4.01–4.07 (ddd, J ¼ J
¼ 10
H
3
1,2
2,3a
Hz, J2,3e ¼ 4 Hz, –CHI–), 4.84–4.90 (ddd, 1H, J ¼ J
¼ 10Hz,
1,2
1,6a
1
3
J1,6e ¼ 5 Hz, –CHCOCH ). CNMR: dC 169.923, 76.745, 37.845, 31.757,
3
3
Found: C, 35.60; H, 4.85%.
1.559, 27.048, 23.584, 21.215. Anal. Calcd. for C H IO : C, 35.82; H, 4.85;
8 13 2
2
Trans-1-acetoxy-2-iodocyclooctane: 2.78 g, 94%. IR (cm ): 1734,
1
1
243, 1047, 410. HNMR: dH 2.07 (s, –COCH ), 4.38–4.43 (ddd,
1
3
J1,2 ¼ J
¼ 6 Hz, J2,3e ¼ 3 Hz, –CHI–), 5.19–5.23 (ddd, 1H,
2,3a
1,6a
1
3
J1,2 ¼ J
¼ 8 Hz, J
¼ 4 Hz, –CHCOCH ).
CNMR: dC 169.919,
1,6e
3
80.446, 37.891, 33.167, 32.438, 26.801, 25.840, 25.589, 25.264,
21.227. Anal. Calcd. for C H IO : C, 40.54; H, 5.74; Found: C, 40.35; H,
5.58%.
1
0
17
2
2
1
Trans-1-acetoxy-2-iodocyclododecane: 3.17 g, 90%. IR (cm ): 1745,
1
238, 416, 721. HNMR: dH 2.09 (s, –COCH ), 4.33–4.40 (ddd,
1
3
J1,2 ¼ J
¼ 6 Hz, J
¼ 12 Hz, –CHI–), 4.83–4.87 (dd, 1H, J
¼
2,3a
2,3e
1,2
1
3
J1,6a ¼ 6 Hz, J
¼ 11 Hz, –CHCOCH ). CNMR: d 170.226, 72.653,
1,6e
3
C
3
5.542, 34.994, 30.329, 28.548, 24.809, 24.401, 24.147, 23.628, 23.003,
1.948, 21.087, 20.660. Anal. Calcd. for C H IO : C, 47.73; H, 7.1;
Found: C, 47.59; H, 7.3%.
2
1
4
25
2
2
1
PhCH(OAc)CH I: 2.38 g, 82%. IR (cm ): 1755, 1233, 1062, 545.
2
1
HNMR: dH 2.14 (s, –COCH ), 3.46–3.49 (dd, J ¼ 4 Hz, J ¼ 8 Hz,
3
–
CH I–), 5.86–5.90 (dd, 1H, J ¼ 5 Hz, J ¼ 8 Hz, –CHCOCH ), 7.36–
2
3
1
.37 (m, 5H, Ph). CNMR: dC 169.768, 138.427, 128.746, 128.700,
3
7
1
3
26.411, 75.160, 21.051, 7.833. Anal. Calcd. for C H IO : C, 41.38; H,
2
1
0
11
.79; Found: C, 41.12; H, 3.93%.
PhC(Me)(OAc)CH I: 2.43 g, 80%. IR (cm ): 1734, 1243, 1031,
1
45. HNMR: dH 2.08 (s, CH ), 2.09 (s, –COCH ), 3.25–3.28
2
1
2
5
3
3
1
3
(
dd, J ¼ 2.5 Hz, J ¼ 5 Hz, –CH I–), 7.26 (s, 5H, Ph). CNMR: dC
2
1
1
4
69.387, 142.027, 128.519, 127.758, 124.709, 80.908, 26.217, 22.020,
7.159. Anal. Calcd. for C H IO : C, 43.42; H, 4.28; Found: C, 43.27; H,
1
1
13
2
.25%.
-Iodo-3-acetoxy-2, 3-dimethylbutane: 2.51 g, 93%. IR (cm ): 1719,
2
1
2
1
1
279, 1166, 410. HNMR: dH 1.29 [s, 6H, (CH ) C(COCH )–], 1.54
3 2 3
1
3
[
s, (CH ) CI–], 2.20 (s, –COCH ). CNMR: d 170.213, 82.731, 30.845,
3 2 3 C

Regioselective Synthesis of a-Iodoacetates
4481
28.156, 24.239, 18.352. Anal. Calcd. for C H IO : C, 35.56; H, 5.56; Found:
C, 35.33; H, 5.52%.
8
15
2
2
-Iodo-2-acetoxyhexane: 2.57 g, 95%. IR (cm ): 1719, 1259, 1031,
1
1
1
4
15. HNMR: d 2.08 (s, –COCH ), 3.22–3.37 (dd H , dd H , J ¼ 5 Hz,
H
3
A
B
J ¼ 10 Hz, –CH H I–), 4.66–4.72 (quin, 1H, J ¼ 6 Hz, –CHCOCH ).
A B 3
13
CNMR: d 170.170, 72.431, 38.004, 28.994, 21.218, 18.477, 13.157,
C
9
.575. Anal. Calcd. for C H IO : C, 35.56; H, 5.56; Found: C, 35.24; H,
15
8
2
5
.29%.
-Iodo-2-acetoxyheptane: 2.56 g, 90%. IR (cm ): 1745, 1243, 1036,
2
1
1
1
4
98. HNMR: d 2.09 (s, –COCH ), 3.22–3.38 (dd H , dd H , J ¼ 5 Hz,
H
3
A
B
J ¼ 10 Hz –CH H I–), 4.67–4.74 (quin, 1H, J ¼ 7 Hz, –CHCOCH ).
A B 3
13
CNMR: d 170.453, 72.403, 31.677, 31.618, 29.087, 21.840, 18.462,
C
1
3.863, 9.651. Anal. Calcd. for C H IO : C, 38.03; H, 5.99; Found: C,
9
17
2
3
7.67; H, 5.64%.
-Iodo-2-acetoxyoctane: 2.71 g, 91%. IR (cm ): 1740, 1243, 1036, 493.
HNMR: dH 2.07 (s, –COCH ), 3.20–3.39 (dd H , dd H , J ¼ 5 Hz,
2
1
1
1
3
A
B
J ¼ 10 Hz –CH H I–), 4.66–4.72 (quin, 1H, J ¼ 6 Hz, –CHCOCH ).
A
B
3
13
CNMR: d 170.264, 72.437, 34.129, 31.610, 28.941, 28.429, 22.529,
C
20.799, 14.005, 8.216. Anal. Calcd. for C H IO : C, 40.27; H, 6.38;
Found: C, 40.26; H, 6.63%.
1
0
19
2
2
-Iodo-2-acetoxyundecane: 2.96 g, 87%. IR (cm ): 1745, 1243, 1000,
1
1
1
4
20. HNMR: d 2.08 (s, –COCH ), 3.23–3.37 (dd H , dd H , J ¼ 5 Hz,
H
3
A
B
J ¼ 10 Hz –CH H I–), 4.66–4.72 (quin, 1H, J ¼ 6 Hz, –CHCOCH ).
A B 3
13
CNMR: d 170.256, 72.461, 36.510, 34.132, 31.871, 31.043, 29.464,
C
29.271, 28.774, 25.056, 22.656, 14.062, 8.187. Anal. Calcd. for C H IO :
C, 45.88; H, 7.35; Found: C, 46.20; H, 7.42%.
1
3
25
2
2
- Iodo -2- acetoxydodecane: 3.29 g, 93%. IR (cm ): 1750, 1238, 1031,
1
1
1
4
16. HNMR: d 2.11 (s, –COCH ), 3.23–3.38 (dd H , dd H , J ¼ 5 Hz,
H
3
A
B
J ¼ 10 Hz –CH H I–), 4.66–4.74 (quin, 1H, J ¼ 5 Hz, –CHCOCH ).
A B 3
13
CNMR: d 170.268, 72.482, 36.522, 34.137, 31.898, 31.043, 29.555,
C
29.413, 29.297, 28.779, 25.056, 22.665, 14.065, 8.183. Anal. Calcd. for
C H IO : C, 47.46; H, 7.92; Found: C, 47.7; H, 7.92%.
1
4
27
2
ACKNOWLEDGMENT
Yi Yi Myint thanks the Ministry of Education, Government of Myanmar;
the Bangalore University, Bangalore; Professor A. Srikrishna, Chairman,
1
3
1
Dept. of Organic Chemistry, I I Sc., Bangalore for C, HNMR spectra and
elemental analysis of all the products and the Indian Council for Cultural
Relations for a fellowship and financial assistance.

4
482
Myint and Pasha
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Received in India August 23, 2004