Hypervalent iodine in synthesis. 66. One pot preparation of β-keto sulfones by reaction of ketones, [hydroxy(tosyloxy) iodo] benzene, and sodium sulfinates

Article abstract of DOI:10.1081/SCC-100105890

One pot reactions of ketones, [hydroxy(tosyloxy)iodo] benzene and sodium sulfinates lead to the formation of the corresponding β-keto sulfones under mild conditions and in good yield.

Full text of DOI:10.1081/SCC-100105890

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HYPERVALENT IODINE IN SYNTHESIS. 66. ONE POT
PREPARATION OF β-KETO SULFONES BY REACTION OF
KETONES, [HYDROXY(TOSYLOXY) IODO] BENZENE,
AND SODIUM SULFINATES
Yuan-Yuan Xie a & Zhen-Chu Chen b
a Department of Chemistry , Zhejiang University (Xi-Xi campus) , Hangzhou, 310028, P.
R. China
b Department of Chemistry , Zhejiang University (Xi-Xi campus) , Hangzhou, 310028, P.
R. China
Published online: 16 Aug 2006.
To cite this article: Yuan-Yuan Xie & Zhen-Chu Chen (2001) HYPERVALENT IODINE IN SYNTHESIS. 66. ONE POT
PREPARATION OF β-KETO SULFONES BY REACTION OF KETONES, [HYDROXY(TOSYLOXY) IODO] BENZENE, AND SODIUM
SULFINATES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 31:20, 3145-3149, DOI: 10.1081/SCC-100105890
To link to this article: http://dx.doi.org/10.1081/SCC-100105890
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SYNTHETIC COMMUNICATIONS, 31(20), 3145–3149 (2001)
HYPERVALENT IODINE IN SYNTHESIS.
66. ONE POT PREPARATION OF
b-KETO SULFONES BY REACTION
OF KETONES, [HYDROXY(TOSYLOXY)
IODO] BENZENE, AND SODIUM
SULFINATES
Yuan-Yuan Xie and Zhen-Chu Chen*
Department of Chemistry, Zhejiang University
(Xi-Xi campus), Hangzhou, 310028, P. R. China
ABSTRACT
One pot reactions of ketones, [hydroxy(tosyloxy)iodo]
benzene and sodium sulfinates lead to the formation of the
corresponding b-keto sulfones under mild conditions and in
good yield.
The sulfonyl group is increasingly attracting attention as a useful
functionality in organic synthesis. b-Keto sulfones occupy a premier
position as derivatives of sulfones and display a broad range of synthetic
versatility.1–5 One particularly well-recognized application of the b-keto
*Corresponding author.
3145
Copyright & 2001by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
3146
XIE AND CHEN
sulfone moiety in synthesis is in a-alkylation with subsequent reductive
desulfurization.6
According to the importance of b-keto sulfones in organic synthesis,
there are many methods available for their synthesis, including Thorpe
reaction of cyano Sulfones,7 oxidation of corresponding b-ketone sulfides
or sulfoxides,8 Claisen condensations of esters with dimethyl sulfone9 and
substitution of a-haloketones with sodium sulfinates.10 But these methods
are deficient in some respects, such as the use of strong base, strict reaction
conditions, toxic reagent, and not readily available starting materials. It is
necessary to develop a new, effective method for the synthesis of b-keto
sulfones.
There is considerable current interest and research activity in hyper-
valent iodine compounds.11 It has been demonstrated that the [hydroxy
(tosyloxy)iodo] benzene (HTIB, 2) is a versatile reagent in organic synthesis
and especially useful is the reaction of HTIB with ketones leading to
tosyloxylketones. This reaction followed by treatment with appropriate
nucleophilies in situ offers a variety of valuable synthetic methods. It pro-
moted us to examine the a-tosyoxylation of ketones with HTIB followed
by treatment with sodium sulfinates. Such reaction would provide a new,
effective method for synthesis of b-keto sulfones without use of lachryma-
tory and toxic a-halohetones.
Here we report a mild, one-pot conversion of ketones to the corre-
sponding b-keto sulfones through treatment of ketones with HTIB and
sodium sulfinate successively (Scheme 1).
Scheme 1.
First, ketone reacts with HTIB to produce a-tosyloxy ketone 3 that
then reacts with sodium sulfinate to give corresponding b-keto sulfone. The
results are summarized in Table 1. Solvent is an important factor for this
reaction. In the first step, reaction can complete smoothly in acetonitrile, but
in the second step, the reaction proceeds difficultly because of the poor
solubility of sodium sulfinate in acetonitrile, so the addition of some
water is necessary.

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HYPERVALENT IODINE IN SYNTHESIS. 66
Table 1. Synthesis of b-Keto Sulfones (4)
3147
Yielda
(%)
M.P.b
(ꢀC)
Lit.
M.P. (ꢀC)
R1
R2
H
R3
4a
4b
4c
CH3
-(CH2)4-
CH3CH2
H
H
H
56
32
80
56–57
83–85
oil (GC
99.77%)
9612
121–123
108–110
138–140
118–119
126–128
76–77
5712
85–8613
no report
CH3
4d
4e
4f
4g
4h
4i
4j
4k
4l
C6H5H
H
H
H
H
H
H
CH3
H
H
H
73
H
H
H
H
H
H
CH3
CH3
Cl
92–93
64
60
65
62
60
66
66
80
p-CH3C6H4
p-CH3OC6H4
p-ClC6H4
p-FC6H4
m-NO2C6H4
C6H5
118–11914
11415
141–14214
116–117.516
no report
7717
CH3
C6H5
CH3
C6H5
51–52
5212
108–109
81–82
133–134
11012
4m
4n
54
70
8312
H
Cl
134.512
aIsolated yield based on ketone.
bMelting points are uncorrected.
The reaction was found to be general and applicable to aliphatic or
aromatic ketones. Several aromatic ketones containing various substituents,
such as para-chloro, para-methyl, para-methoxy, meta-nitro were success-
fully reacted. However, this method was not suitable for unsymmetrical
aliphatic ketones, since there was not a desirable regioselectivity for them
in the a-tosyoxylation process.
In conclusion, we have provided a new, effective method for synthesis
of b-keto sulfones. It has some advantages over previous methods, such as
simple procedure, mild reaction conditions and good yields.
EXPERIMENTAL SECTION
IR spectra were recorded as KBr pellets on PE-683 Infrared Spectro-
photometer. 1H-NMR spectra were recorded on PMK-60 Spectrometer
using CCl4 as the solvent with TMS as an internal standard. MS was
recorded on HP-5989B Mass Spectrometer. Elemental analysis was per-
formed on a Carlo Zrba EA 1106 instrument. GC Purity was recorded on
Schimadzu GC-16A.

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XIE AND CHEN
Typical Procedure for Synthesis of
1-Phenyl-2-(Phenylsulfonyl) Ethanone (4d)
Acetophenone (0.12 g, 1mmol) and HTIB (0.392 g, 1mmol) were
added successively with efficient stirring to acetonitrile (5 mL). The reaction
mixture was refluxed for 40 min, then sodium phenylsulfinate (0.4 g, 2 mmol)
and water (1mL) were slowly added. The mixture was refluxed for 2 h.
Subsequently, the reaction mixture was poured into water (20 mL) and
extracted with dichloromethane (3 ꢁ 10 mL). The combined organic phase
was dried with anhydrous magnesium sulfate, filtered and evaporated under
reduced pressure. The crude product was purified by preparative TLC (ace-
tate/cyclohexane ¼ 1:3) to obtain 4d (0.19 g, 73% yield) as white solide.
Spectroscopic Data
1
4a. IR (cmÀ1) 1740 (C¼O), 1295, 1155 (O ¼ S ¼ O). H-NMR, ppm:
d 2.40 (s, 3H), 4.07 (s, 2H), 7.57–8.24 (m, 5H).
4b. IR (cmÀ1) 1719 (C¼O), 1309, 1144 (O¼S¼O). 1H-NMR,
ppm: d 1.35–2.75 (m, 8H), 3.73 (t, 1H), 7.35–7.88 (m, 5H).
1
4c. IR (cmÀ1) 1721 (C¼O), 1309, 1150 (O¼S¼O). H-NMR, ppm:
d 0.9 (t, 3H), 1.25 (d, 3H), 2.45–2.81 (q, 2H), 4.03–4.40 (q, 1H), 7.41–8.03
(m, 5H). MS m/z 226 (Mþ, 4.97), 85 (5.27), 141 (11.92), 57 (100.00). GC
Purity: 99.77%.
4d. IR (cmÀ1) 1690 (C¼O), 1320, 1160 (O¼S¼O). 1H-NMR,
ppm: d 4.70 (s, 2H), 7.37–8.27 (m, 10H).
1
4e. IR (cmÀ1) 1680 (C¼O), 1300, 1165 (O¼S¼O). H-NMR, ppm:
d 2.43 (s, 3H), 4.55 (s, 2H), 7.16–8.10 (m, 9H).
4f. IR (cmÀ1) 1680 (C¼O), 1310, 1160 (O¼S¼O). H-NMR, ppm:
1
d 3.84 (s, 3H), 4.48 (s, 2H), 6.68–8.21(m, 9H).
4g. IR (cmÀ1) 1705 (C¼O), 1305, 1140 (O¼S¼O). 1H-NMR,
ppm: d 4.57 (s, 2H), 7.40–8.27 (m, 9H).
4h. IR (cmÀ1) 1687 (C¼O), 1315, 1165 (O¼S¼O). H-NMR, ppm:
1
d 4.59 (s, 2H), 6.97–8.07 (m, 9H).
4i. IR (cmÀ1) 1700 (C¼O), 1318, 1152 (O¼S¼O). H-NMR, ppm:
1
d 4.71(s, 2H), 7.51–8.81(m, 9H). Elemental Analysis: Calculated C,
55.08; H, 3.63; N, 4.59. Found C, 54.94; H, 3.73; N, 4.65.
4j. IR (cmÀ1) 1690 (C¼O), 1310, 1145 (O¼S¼O). 1H-NMR,
ppm: d 1.50 (d, 3H), 5.15 (q, 1H), 7.40–8.30 (m, 10H).
4k. IR (cmÀ1) 1736 (C¼O), 1340, 1150 (O¼S¼O). H-NMR, ppm:
1
d 2.24 (s, 3H), 2.37 (s, 3H), 2.48 (s, 3H), 4.04 (s, 2H), 7.20–7.94 (m, 4H).

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HYPERVALENT IODINE IN SYNTHESIS. 66
3149
1
4l. IR (cmÀ1) 1695 (C¼O), 1327, 1156 (O¼S¼O). H-NMR, ppm:
d 2.33 (s, 3H), 4.60 (s, 2H), 7.13–8.20 (m, 9H).
4m. IR (cmÀ1) 1735 (C¼O), 1316, 1150 (O¼S¼O). 1H-NMR,
ppm: d 2.32 (s, 3H), 4.08 (s, 2H), 7.21–7.97 (m, 4H).
1
4n. IR (cmÀ1) 1700 (C¼O), 1315, 1146 (O¼S¼O). H-NMR, ppm:
d 4.65 (s, 2H), 7.23–8.10 (m, 9H).
REFERENCES
1. Magnus, P.D. Tetrahedron 1977, 33, 2019.
2. Kurth, M.J.; O’Brien, M.J. J. Org. Chem. 1985, 50, 3846.
3. Lansbury, P.T.; Bebernitz, G.E.; Maynard, S.C.; Spagnuolo, C.J.
Tetrahedron Lett. 1985, 26, 169.
4. Mandai, T.; Yanagi, Y.; Araki, K.; Morisaki, Y.; Kawada, M.;
Otera, J. J. Am. Chem. Soc. 1984, 106, 3670.
5. House, H.O.; Larson, J.K. J. Org. Chem. 1968, 33, 61 .
6. Fujii, Masayuki; Nakamura, Kaoru; Mekata, Hideyuki; Oka,
Shinzaburo; Ohno, Atsuyoshi Bull. Chem. Soc. Jpn. 1988, 61, 495.
7. Truce, W.E.; Bannister, W.W.; Knospe, R.H. J. Org. Chem. 1962,
27, 2821.
8. Trost, B.M.; Curran, D.P. Tetrahedron Lett. 1981, 22, 1287.
9. Truce, W.E.; Knospe, R.H. J. Am. Chem. Soc. 1955, 77, 5063.
10. Tkoger; Ungar, J. Prakt. Chem. 1926, 112, 243.
11. (a) Kitamura, T.J. Synth. Org. Chem. Jpn. 1995, 53, 893. (b) Stang,
P.J.; Zhdankin, V.V. Chem. Rev. 1996, 46, 1123. (c) Kitamura, T.;
Fujiwara, Y. Org. Prep. Proced. Int. 1997, 29, 409. (d) Wirth, T.;
Hirt, U.H. Synth. 1999, 8, 1271.
12. Suter, C.M. The Organic Chemistry of Sulfur, John Wiley, New York,
1945, 721.
13. Winternitz, F.; Antia, N.J.; Tumlirova, M.; Lachazette, R. Bull. Soc.
Chim. France 1956, 1817.
13. Liangsheng, Wang; Hui, li; Xiaojiang, Wang; Zheng, Zhang
Environmental Chemistry (China.) 1993, 12, 151. cf. C.A.: 1993, 119,
256088q.
14. Btaiw, S.H.; Lssa, Y.M.; El-ansary, A.L. J. Indian Chem. Soc. 1983,
60, 137.
15. Amel, R.T.; Marek, P.J. J. Org. Chem. 1973, 38, 3513.
16. Lamn, B.; Samuelsson, B. Acta. Chem. Scand. 1970, 24, 561.
Received in the Netherlands January 2, 2001

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