New preparative opportunities provided by iodosobenzene diacetate in reactions with alkenes

Full text of DOI:10.1023/A:1013156801567

Russian Journal of Organic Chemistry, Vol. 37, No. 8, 2001, pp. 1179 1181. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 8, 2001,
pp. 1238 1239.
Original Russian Text Copyright
2001 by Yusubov, Zholobova.
SHORT
COMMUNICATIONS
New Preparative Opportunities Provided by Iodosobenzene
*
Diacetate in Reactions with Alkenes
M. S. Yusubov1 and G. A. Zholobova2
,2
1
Siberian State Medical University, Tomsk, 634050 Russia
Tomsk Polytechnic University, Tomsk, 634050 Russia
2
Received February 15, 2001
The great interest in compounds of polyvalent
iodine is due to their versatile synthetic properties.
Within last three decades quite a number of reviews
and several monographs were published concerning
unique transformations involving these substances
presence of sulfuric acid with styrene (II), 1,1-di-
phenylethylene (III), chalcone (IV), and cyclohexene
(V) gave rise to oxidative rearrangement resulting in
carbonyl compounds or their acetals VI X (see table).
The oxidative rearrangement occurred with com-
pounds II IV under mild conditions (in 15 25 C
range) affording in high preparative yields (80 94%)
compounds VI X. The oxidation of cyclohexene V
is accompanied with cycle contraction yielding
aldehyde X as the main reaction product. Using
GC-MS method we detected 1,2-dimethoxycyclo-
hexane and 1-methoxy-1-cyclohexene as side pro-
ducts.
[1 5]. The reactions of organic derivatives of
iodine(III) with alkenes are among the most extensive-
ly investigated; depending on the reaction conditions
they afford products of addition, oxidation, or re-
arrangement [1 7]. The iodosobenzene diacetate in
contrast to the majority of related compounds is low-
electeophilic substance and under common conditions
does not react with alkenes.
We found that the reaction of iodosobenzene
diacetate (I) in methanol or acetonitrile in the
These oxidative rearrangements of compounds
II V were previously performed by treating with
Reaction conditions, yields and characteristics of reaction products obtained from iodosobenzene diacetate and alkenes
II V, XI, XIII
Reaction
product
Time,
min
Temperature,
C
Yield,
%
Substrate
bp or mp,
C
a
II
II
VI
20
20
30
320
140
320
300
20
15
15
25
15
87
217 220 (750 mm Hg) {219 221 (754 mm Hg) [7]}
b,c
VII
VIII
IX
X
XII
XIV
80
'
III
IV
V
XI
XIII
94
90
42
59
32
59 60 (60 [8])
97 98 (94 [7])
e
e
g
15
25
48 50 (MeOH H O)
2
h
a
b
c
d
e
f
Isolated by column chromatography on Al O .
2
3
In acetonitrile with the use of 50% aqueous H SO .
2
4
Isolated in the form of 2,4-dinitrophenylhydrazone, mp 120 121 C (120 C [8]).
The reaction temperature was gradually raised to 0 C.
Stirred for 20 min at 15 C, then at 20 C.
Isolated in the form of 2,4-dinitrophenylhydrazone, mp 154 156 C (156 157 C [9]).
Stirred for 20 min at 15 C, then at 20 C.
Isolated in the form of 2,4-dinitrophenylhydrazone, mp 236 238 C (236 237 C [8]).
g
h
*
The study was carried out under financial support of the Russian Foundation for Basic Research (grant no. 00-03-32812a).
1
070-4280/01/3708-1179$25.00 2001 MAIK Nauka/Interperiodica

1
180
YUSUBOV, ZHOLOBOVA
C H IO in methanol in the presence of acids
cooled to the temperature indicated in the table was
added 2.02 mmol of iodosobenzene diacetate (I), and
dropwise while stirring was added 0.45 0.5 ml of
6
5
(
CF SO H, FSO H, BF Et O), C H I(OH)OTs,
3 3 3 3 2 6 5
phenyl iodosulfate and iodobenzene bis(trifluoro-
acetate), but the yields of the reaction products were
considerably lower (20 60%) [6, 7, 10, 11].
5
0% solution of H SO in methanol. The mixture was
2 4
kept at the indicated temperature for the time interval
mentioned in the table, then poured into 30 ml of
water, extracted with ethyl ether (2 30 ml), washed
with saturated aqueous NaCl solution, and dried on
Na2SO4. The ether was distilled off, the residue was
dissolved in benzene and subjected to chromato-
graphy on a column packed with silica gel (eluent
hexane, then hexane benzene, 4: 1). 3,4-Dimethoxy-
It is important that with (E,E)-1,4-diphenylbuta-
diene (XI) the oxidative rearrangement did not occur
but in 59% yield was obtained 1,2-dimethoxylation
product, 3,4-dimethoxy-1,4-diphenyl-1-butene (XII).
In earlier publications [2, 12] was reported only on
reactions of C H I(OH)OTs with conjugated dienes
6
5
(
1,3-butadiene, isoprene, 2,4-hexadiene, and cyclo-
hexadiene) furnishing only 1,4-addition products in
low yield. In [12] the reaction of 1,3-butadiene with
Zefirov reagent [ -oxo-bis(trifluoromethanesulfonyl-
oxy)iodobenzene] gave rise to intractable mixture of
1,4-diphenyl-1-butene (XII). IR spectrum (CCl ), ,
4
1
1
cm : 1140 (C O C). H NMR spectrum (CDCl ), ,
3
ppm: 3.24 s (3H, OMe), 3.26 s (3H, OMe), 3.78 d.d
(
1H, =CHCHOMe, J 4.9, 7.7 Hz), 4.24 d (1H,
PhCHOMe, J 4.9 Hz), 6.15 d.d (1H, PhHC=CH, J
.7, 16.1 Hz), 6.40 d (1H, PhHC=CH, J 16.1 Hz),
1
,2- and 1,4-addition products in 11: 89 ratio [12].
7
We failed to perform selectively the oxidative
rearrangement of (E)-stilbene (XIII) under the action
of iodosobenzene diacetate. In all cases in the reaction
products prevailed benzophenone (XIV), and by
GC-MS method were detected diphenylacetaldehyde,
diphenylacetic acid, epoxystilbene, deoxybenzoin,
and benzyl. The nonselectivity of the process is
apparently due to the low solubility of (E)-stilbene
under the reaction conditions.
7.20 7.37 m (10H arom). Found, %: C 80.45; H
7.50. C H O . Calculated, %: C 80.56; H 7.51.
1
8
20
2
The authors are grateful to Professor V. D. Fili-
monov for helpful discussion.
REFERENCES
1
2
. Varvogli, S.A., Synthesis 1984, no. 9, pp. 709 726.
. Moriarty, R.M., Vaid, R.K., and Koser, G.F., Synlett.,
Thus the results obtained show in general new
preparative opportunities opened for iodosobenzene
diacetate, the most accessible compound of the poly-
valent iodine, and call for wider use of the substance
in the organic synthesis.
1
990, no. 7, pp. 365 383.
3
4
. Stang, P.J. and ZhdankinV.V., Chem. Rev., 1996,
vol. 96, no. 3, pp. 1123 1178.
. Wirth, T. and Hirt U.H., Synthesis, 1999, no. 8,
pp. 1271 1287.
Oxo compounds and acetals VI, VII X, XII. To
a solution of 2 mmol of alkene in 6 8 ml of methanol
5. Merkushev, E.B., Doctoral Sci. (Chem.) Dissertation,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

NEW PREPARATIVE OPPORTUNITIES PROVIDED BY IODOSOBENZENE DIACETATE
1181
Tomsk, 1985.
Grotjahn, D.B., Tetrahedron Lett., 1978, vol. 19,
6
7
. Koser, G.F., Rebrovic, L., and Wettach, R.H., J. Org.
Chem., 1981, vol. 46, no. 21, pp. 4324 4326.
. Moriarty, R., Khosrowshashi, J.S., and Prakash, O.,
Tetrahedron Lett., 1985, vol. 26, no. 25,
pp. 2961 2964.
no. 45, pp. 4315 4318.
10. Zefirov, N.S., Keipl, R., Palyulin, V.A., Berglund, B.,
,
Tykvinskii, R., Zhdankin, V.V., and Koz min, A.S.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1988, no. 10,
pp. 1452 1453.
8
9
. Furniss, B.S., Hannaford, A.J., Smith, P.W.G., and
Tatchell, A.R., Vogel s Textbook of Practical Organic
Chemistry, London: Longman, 1989.
. Andersen, N.H., Duffy, P.F., Denniston, A.D., and
11. Miki, Y., Fujita, R., and Matsushita, K.J., J. Chem.
Soc., Perkin Trans. I, 1998, no. 16, pp. 2533 2536.
12. Hembre, R.T., Scott, C.P., and Norton, J.R., J. Org.
Chem., 1987, vol. 52, no. 16, pp. 3650 3654.
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001