Unique Selectivity of Iodohydroxylation Reaction of Allenyl Phenyl Sulfoxides in Aqueous MeCN. A Stereodefined Synthesis of (E)-2-iodo-3-hydroxy-1-alkenyl Sulfoxides

Article abstract of DOI:10.1021/ol006639p

equation presented Iodohydroxylation reaction of allenyl phenyl sulfoxides with I₂ can smoothly proceed to generate (E)-2-iodo-3-hydroxy-1-alkenyl sulfoxides with excellent regio- and stereoselectivity in high or excellent yields. The configura

Full text of DOI:10.1021/ol006639p

ORGANIC
LETTERS
2000
Vol. 2, No. 24
3893-3895
Unique Selectivity of Iodohydroxylation
Reaction of Allenyl Phenyl Sulfoxides in
Aqueous MeCN. A Stereodefined
Synthesis of
(E)-2-Iodo-3-hydroxy-1-alkenyl Sulfoxides
Shengming Ma,* Qi Wei, and Haiming Wang
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China
masm@pub.sioc.ac.cn
Received September 23, 2000
ABSTRACT
Iodohydroxylation reaction of allenyl phenyl sulfoxides with I2 can smoothly proceed to generate (E)-2-iodo-3-hydroxy-1-alkenyl sulfoxides
with excellent regio- and stereoselectivity in high or excellent yields. The configuration of E-2a was determined by the X-ray diffraction study.
Halohydroxylations of carbon-carbon double bond are one
of the most important methods of providing â-halogen-
substituted alcohols,1 since two functional groups, i.e., -X
and -OH, are introduced into substrates at the same time
(Scheme 1). However, for allenes, the regio- and stereo-
the iodohydroxylation of a series of allenyl phenyl sulfoxides
affording the stereodefined (E)-2-iodo-3-hydroxy-1-alkenyl
phenyl sulfoxides in high yields.
During the course of our study on the chemisty of allenes,3
we have developed the highly selective hydrohalogenation
reactions of electron-deficient 1,2-allenes.4 In our continuous
effort toward the highly selective addition reaction of allenes,
it is interesting to observe that the addition reaction of (1,2-
propadienylsulfinyl)benzene (1a) with I2 unexpectedly af-
forded the iodohydroxylation product (E)-3-(phenylsulfinyl)-
2-iodopropenol (E-2a) with excellent regio- and stereo-
selectivity albeit in low yield; the formation of the corre-
Scheme 1
(1) (a) Cabanal-Duvillard, I.; Berrien, J.; Royer, J.; Husson, H. Tetra-
hedron Lett. 1998, 39, 5181. (b) Rossen, K.; Reamer, R. A.; Volante, R.
P.; Reider, P. J. Tetrahedron Lett. 1996, 37, 6843. (c) Mevellec, L.; Evers,
M.; Huet, F. Tetrahedron 1996, 52, 15103. (d) Crossley, M. J.; Davies, S.
R.; Hambley, T. W. Aust. J. Chem. 1994, 47, 2221. (e) Sawyer, D. T.;
Hage, J. P.; Sobkowiak, A. J. Am. Chem. Soc. 1995, 117, 106. (f) Fu, H.;
Kondo, H.; Ichikawa, Y.; Look, G. C.; Wong, C. J. Org. Chem. 1992, 57,
7265. (g) Lai, J.; Wang, F.; Guo, G.; Dai, L. J. Org. Chem. 1993, 58, 6944.
(h) Rodebaugh, R.; Fraser-Reid, B. J. Am. Chem. Soc. 1994, 116, 3155. (i)
Yamashita, M.; Iida, A.; Ikai, K.; Oshikawa, T.; Hanaya, T.; Yamamoto,
H. Chem. Lett. 1992, 407. (j) Miljkovic, D.; Djurendic, E.; Vukojevic, N.;
Gasi, K.; Csanadi, J. Carbohydr. Res. 1992, 233, 251. (k) Kato, T.;
Hirukawa, T.; Namiki, K. Tetrahedron Lett. 1992, 33, 1475.
selectivity would be a formidable challenge to make this type
of methodology synthetically attractive2 unless a factor is
introduced to control the selectiVity! In this Letter, we wish
to report the first protocol for such highly regio- and
stereoselective chemical transformations by introducing a
sulfinyl group into allenes to ensure high selectivities, i.e.,
(2) Bianchini, J.-P.; Cocordano, M. Tetrahedron 1970, 26, 3401.
10.1021/ol006639p CCC: $19.00 © 2000 American Chemical Society
Published on Web 11/10/2000

sponding diiodides 3A and 3B was not observed (Scheme
2). The structure of E-2a was unambiguously established by
the X-ray diffraction study.
as HX),5 bases were added to neutralize the in situ generated
HI. The result with K2CO3 was not satisfactory (entry 3,
Table 1). After trial and error, we found that LiOAc showed
the best result with the exclusive formation of E-2a in 69%
at rt, but 18% of starting material was recovered (entry 6,
Table 1). When the reaction was heated to 55 °C using 2.0
equiv of I2, E-2a was formed in 96% yield within 1 h (entry
8, Table 1). The reaction did not go to completion with 1.5
equiv of I2 even after 4 h at 55 °C (entry 4, Table 1). In
addition, the utilization of 4.0 equiv of water accelerated the
reaction but the yield was lower (entry 7, Table 1).
Scheme 2
Thus, we studied the iodohydroxylation of a series of
allenyl phenyl sulfoxides. Some typical results are sum-
marized in Table 2. The following points are noteworthy:
Table 2. The Reaction of Allenyl Phenyl Sulfoxides with
I2/H2O in Aqueous MeCNa
With the unique selectivity observed for the formation of
E-2a, we tried to optimize the conditions of this iodo-
hydroxylation reaction of 1a using iodine in MeCN-H2O
(7:1). The results are summarized in Table 1. When 2.0 equiv
Table 1. Reaction of (1,2-Propadienylsulfinyl)benzene (1a)
with I2/H2O in Aqueous MeCNa
1
c
entry
R1
R2
R3
I2
time (h) yield (%)d
1b
2
3
4
5
H
H
H
H
H
H (1a )
H (1b)
H (1c)
t-Bu (1d )
Me (1e)
2.4
1.6
1.6
1.2
1.2
1
96
79
82
87
87
74
88
Ph
n-Bu
H
H
H
2.2
1.5
3.2
0.5
0.3
1.3
b
Me
entry I2
additives time (h) temp (°C) yield (%)c 1a d (%)
6
7
(CH2)5 (1f) 1.2
Me (1g) 1.2
1
2
3
4
5
6
7e
8
1.0
2.0
5
4
4
4
2.5
5
0.2
1
rt
rt
rt
55
65
rt
55
55
49
66
3.9
62
64
69
60
96
34
0
84
29
0
18
0
0
n-Bu
Me
a The reaction was carried out using allenyl phenyl sulfoxide (0.5 mmol),
I2 (see Table 2), and LiOAc (1 mmol) in MeCN-H2O (1 mL, v/v ) 7:1)
at room temperature. b The reaction was carried out at 55 °C. c Equivakents
of iodine used. d Isolated yield of E-2 based on 1.
2.0 K2CO3
1.5 LiOAc
2.0 NaHCO3
2.0 LiOAc
2.0 LiOAc
2.4 LiOAc
(1) The iodohydroxylation reactions of C-aryl- or C-alkyl-
substituted allenyl phenyl sulfoxides were faster than that
of the unsubstituted 1a, and the reactions finished in from
0.3 to 3.2 h at room temperature (compare entries 2-7 with
1, Table 2). (2) The yields of the corresponding products 2
are high yields and the regio- and stereoselectivity of this
reaction are excellent. (3) When 1d with a de ratio of 93:7
was used the corresponding iodohydroxylation product E-2d
was formed in the same diastereomeric ratio as determined
a The reaction of allenic sulfoxide (1a, 1 mmol) with I2 was carried out
in MeCN-H2O (2 mL/0.3 mL). b Equivalents of iodine used. c Isolated yield
based on 1a. d Yield of recovered 1a. e Only 4.0 equiv of H2O was used.
of iodine was used, the reaction was complete in aqueous
MeCN within 4 h to afford the product E-2a in 66% yield
(entry 2, Table 1) together with some byproducts of low
polarity. Since the iodohydroxylation product (E-2a) and HI
were formed at the same time, and allenyl phenyl sulfoxides
are sensitive to even a small amount of strong acids (such
1
by H NMR spectra and HPLC (entry 4, Table 2).
Generally the iodohydroxylation of carbon-carbon double
bond directly using I2 and H2O is difficult.6 Reaction of
allenes or 2,3-allenic esters with halogens was known to form
(3) (a) Ma, S.; Shi, Z. J. Org. Chem. 1998, 63, 6387. (b) Ma, S.; Duan,
D.; Shi, Z. Org. Lett. 2000, 2, 1419. (c) Ma, S.; Zhao, S. J. Am. Chem.
Soc. 1999, 121, 7943. (d) Ma, S.; Shi, Z.; Yu, Z. Tetrahedron Lett. 1999,
40, 2393. (e) Ma, S.; Zhang, J. Chem. Commun. 2000, 117. (f) Ma, S.; Li,
L. Org. Lett. 2000, 2, 941. (g) Ma, S.; Wu, S. J. Org. Chem. 1999, 64,
9314.
(4) (a) Ma, S.; Li, L.; Xie, H. J. Org. Chem. 1999, 64, 5325. (b) Ma, S.;
Shi, Z.; Li, L. J. Org. Chem. 1998, 63, 4522. (c) Ma, S.; Wang, G. Chin.
J. Chem. 1999, 17, 545. (d) Ma, S.; Wei, Q. J. Org. Chem. 1999, 64, 1026.
(e) Ma, S.; Wei, Q. Eur. J. Org. Chem. 2000, 1939.
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3; Pergamon Press: Oxford, 1979; p 130.
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Nun˜ez, M. E. Org. Lett. 1999, 1, 2125. (b) Masuda, H.; Takase, K.; Nishio,
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3894
Org. Lett., Vol. 2, No. 24, 2000

dihalogenation products.7 Even under our reaction conditions,
the diiodination product 1,2-diiodo-2-decene with a configu-
rationally isomeric ratio of 88:12 was formed (Scheme 3).
The introduction of the sulfinyl group must be the key for
the control of selectivities.
operation, and ready elaboration of the functional groups in
the products,9 the reaction shows its broad utility in organic
synthesis. In addition, with different nucleophiles and a
search for different groups which are capable of controlling
the pertinent selectivities, this protocol will open up a new
area for the highly selective synthesis of functionalized
stereodefined alkenes. Further studies on the scope, the
mechanism of iodohydroxylation of 1.2-allenic sulfoxides,
and the synthetic applications of this reaction are being
carried out in our laboratory.
Scheme 3
Acknowledgment. We are grateful to the Chinese
Academy of Sciences and Shanghai Municipal Committee
of Science and Technology for financial support. Shengming
Ma is the recipient of a 1999 Qiu Shi Award for Young
Scientific Workers issued by Hong Kong Qiu Shi Foundation
of Science and Technology (1999-2002) and a Special
Starting Grant for Outstanding Young Chemists issued by
the National Natural Science Foundation of China (29525202)
In conclusion, we have observed the unique regio- and
stereoselectivity in the iodohydroxylation reaction of allenyl
phenyl sulfoxides, which provides an efficient entry to (E)-
2-iodo-3-hydroxy-1-alkenyl sulfoxides. Because of the easy
availability of the starting materials,8 simple/convenient
Supporting Information Available: Typical experimen-
tal procedure and analytical data for all the products. This
material is available free of charge via the Internet at
http://pubs.acs.org.
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OL006639P
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