Synthesis of symmetrical sulfones from rongalite: Expansion to cyclic sulfones by ring-closing metathesis

Article abstract of DOI:10.1002/ejoc.200500264

A simple method for the synthesis of symmetrical sulfones using rongalite has been developed. Terminally olefinic sulfone derivatives were subjected to ring-closing metathesis (RCM) reactions to generate cyclic sulfones. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejoc.200500264

FULL PAPER
Synthesis of Symmetrical Sulfones from Rongalite: Expansion to Cyclic
Sulfones by Ring-Closing Metathesis
[a]
[a]
[a]
Sambasivarao Kotha,* Priti Khedkar, and Arun Kumar Ghosh
Keywords: Rongalite / Ring-closing metathesis / Sulfones / Sulfur heterocycles
A simple method for the synthesis of symmetrical sulfones
using rongalite has been developed. Terminally olefinic sul-
fone derivatives were subjected to ring-closing metathesis
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
(RCM) reactions to generate cyclic sulfones.
Introduction
ple, the open chain, terminal-olefin-containing symmetrical
sulfones (7–10), were conveniently prepared by treating
various alkyl bromides of different chain length with an ex-
cess amount of rongalite in the presence of potassium car-
bonate and the phase-transfer catalyst (PTC) tetrabutylam-
monium bromide (Scheme 1).
Sulfones are useful synthons for the construction of car-
bon–carbon bonds via anionic, cationic, and radical inter-
[
1]
mediates. Fused or 3-substituted sulfolenes are a latent
source of conjugated dienes. Therefore, they are useful part-
ners in Diels–Alder reactions for the synthesis of complex
[
2]
synthetic targets containing six-membered rings. Due to
the electron-withdrawing nature of the sulfone moiety,
neighboring methylene or methyl group(s) can be alkylated
with various electrophiles. This unique reactivity coupled
with the ease of desulfonylation has been exploited in se-
veral instances for the construction of various theoretically
interesting and biologically active molecules.[ Moreover, α-
halogenated sulfones are valuable precursors for the Ram-
berg–Bäcklund reaction.[ In view of the varied applica-
tions, sulfone derivatives are the preferred starting materials
for diversity-oriented synthesis.
3]
Scheme 1.
The possible mechanism for the formation of sulfone de-
rivatives is shown in Scheme 2. The reaction involves nucle-
ophilic displacement by the hydroxymethanesulfinate
anion, followed by the loss of a formaldehyde molecule in
the presence of a base, thus generating a nucleophile for the
second alkylation step.
4]
Although sulfones are used widely in organic synthesis,[5]
most of the methods involve multistep synthetic se-
[
6]
quences. The importance of sulfones encouraged us to se-
arch for alternate synthetic routes. In this context, we iden-
tified rongalite as a readily available source of the sulfoxyl-
ate dianion. Rongalite (trade name for sodium hydroxy-
methanesulfinate or sodium formaldehydesulfoxylate) is
commonly used in the textile industry as a decolorizing
agent. Although there are few reports demonstrating the
2
– [7]
utility of rongalite as a source of SO2
,
it has remained
dormant in synthetic organic chemistry.
Results and Discussion
Herein we report our preliminary results for the synthesis
of symmetrical sulfones in a one-pot procedure. For exam- Scheme 2. Proposed mechanism for the formation of sulfone deriv-
atives.
[
a] Department of Chemistry, Indian Institute of Technology-Bom-
bay,
To test the feasibility of this methodology in intramol-
ecular systems, 1,8-bis(bromomethyl)naphthalene (5) was
treated with rongalite and potassium carbonate under PTC
Powai, Mumbai-400 076, India
Fax: +91-22-2572 3480
E-mail: srk@chem.iitb.ac.in
Eur. J. Org. Chem. 2005, 3581–3585
DOI: 10.1002/ejoc.200500264
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3581

S. Kotha, P. Khedkar, A. K. Ghosh
FULL PAPER
conditions. We were pleased to obtain the corresponding fone 13. Along similar lines, sulfone 14 was obtained in
sulfone 11 in good yield. Subsequently, under the same re- 97% yield starting with 8 (Scheme 3).
action conditions, 2,2Ј-bis(bromomethyl)-1,1Ј-biphenyl (6)
gave the corresponding sulfone 12. Various sulfone deriva-
tives prepared are listed in Table 1.
Table 1. Sulfone derivatives prepared from rongalite.
Scheme 3.
To our surprise, the RCM reaction of the sulfone deriva-
tive 9 with both the catalysts A and B gave a diastereomeric
mixture of the 18-membered macrocyclic bis-sulfone 15.
This dimer was found to be sparingly soluble in ethyl ace-
tate. All attempts to purify the product by column
chromatography resulted in poor recovery. Eventually, the
difference in solubility of the macrocyclic bis-sulfone in
ethyl acetate and chloroform was exploited for its purifica-
tion. A short pad of silica gel was charged with the crude
reaction mixture and washed with chloroform. The wash-
ings were concentrated, and the residue obtained after the
removal of chloroform was rinsed with a cold ethyl acetate/
petroleum ether mixture (10:1) two to three times to remove
trace impurities of the catalyst. The purified product was
obtained in moderate yield. Subsequently, the dia-
stereomeric mixture of the 22-membered macrocyclic bis-
sulfone 16 was obtained, starting with 10, in a similar man-
ner (Scheme 4).
Acyclic sulfones 7–10 appear to be ideal candidates for
the synthesis of cyclic sulfone derivatives by the ring-closing
[
8,9]
metathesis (RCM) reaction. In recent years, metathesis
has emerged as a powerful synthetic tool for the construc-
tion of various carbo-, hetero- and macrocyclic compounds.
Scheme 4.
The ruthenium–carbene catalysts A[ and B (Figure 1),
developed by Grubbs and coworkers, have attracted a great
deal of attention due to their broad functional group toler-
ance.
10]
[11]
In view of the less favorable free-energy changes associ-
ated with the formation of 9- and 11-membered rings, the
hypothetical ligating interactions between the sulfonyl oxy-
Figure 1. Ruthenium-based olefin metathesis catalysts.
The compatibility of sulfonamide and sulfamide func-
tionalities with ruthenium-based catalysts is well-estab-
[
12,13]
lished.
However, applications of RCM for the synthesis
[14]
of cyclic sulfones are relatively rare. The diallyl sulfone 7
was treated with Grubbs catalyst A in refluxing dichloro-
methane to give a 97% isolated yield of the butadiene sul- Figure 2. Possible mechanism for the formation of sulfone dimers.
3582 © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org Eur. J. Org. Chem. 2005, 3581–3585

Synthesis of Symmetrical Sulfones from Rongalite: Expansion to Cyclic Sulfones
gens and the ruthenium center[15] can account for the for- Preparation of Compound 8: A suspension of rongalite (1.73 g,
FULL PAPER
1
1.23 mmol), potassium carbonate (1.55 g, 11.23 mmol), tetrabu-
tylammonium bromide (35 mg, 0.11 mmol), and 4-bromo-1-butene
(300 mg, 2.25 mmol) in DMF (25 mL) was stirred at room tem-
mation of dimers. The structural rigidity induced by this
chelating effect may be responsible for the formation of one
of the diastereomers as the major product (Figure 2).
2
perature for 72 h and then quenched with cold water (15 mL). The
aqueous phase was extracted with diethyl ether (3×50 mL). The
organic layer was washed with water and brine, dried with anhy-
drous sodium sulfate, and concentrated. The crude compound was
purified by silica gel column chromatography. Elution of the col-
umn with a 10% ethyl acetate/petroleum ether mixture gave the
Conclusion
We believe that this method should serve as a useful ad-
dition to the existing methods for the synthesis of sulfones.
Overall, a simple and economical procedure has been devel-
compound 8 (106 mg, 54%) as a colorless liquid. IR (neat): ν˜ max
1
=
–1
1
643, 1446, 1321, 1137, 926 cm . H NMR (400 MHz, CDCl
3
): δ
oped for the synthesis of symmetrical sulfone derivatives, = 2.57–2.63 (m, 4 H), 3.03–3.07 (m, 4 H), 5.11–5.19 (m, 4 H), 5.77–
1
3
and this protocol should find its way in organic synthesis 5.87 (m, 2 H) ppm. C NMR (100.6 MHz, CDCl
3
): δ = 26.2, 52.3,
for carbon–carbon-bond-forming reactions. Efforts are un- 117.7, 134.0 ppm. HRMS: m/z: (M + 1)+ found 175.0798; calcd.
for C
8 15 2
H O S 175.0793.
derway in our laboratory towards the expansion of the
chemistry described here.
Preparation of Compound 9: A suspension of rongalite (1.54 g,
10.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), tetrabu-
tylammonium bromide (32 mg, 0.1 mmol), and 5-bromo-1-pentene
3 (300 mg, 2.01 mmol) in DMF (25 mL) was stirred at room tem-
perature for 72 h and then quenched with cold water (15 mL). The
aqueous phase was extracted with diethyl ether (3×50 mL). The
organic layer was washed with water and brine, dried with anhy-
drous sodium sulfate, and concentrated. The crude compound was
purified by silica gel column chromatography. Elution of the col-
umn with a 10% ethyl acetate/petroleum ether mixture gave the
compound 9 (120 mg, 59%) as a colorless solid having a low melt-
Experimental Section
General Remarks: Analytical TLC was performed on (10×5 cm)
glass plates coated with silica gel G or GF 254 (containing 13%
CaSO
4
as a binder). Visualization of the spot on the TLC plate
vapor or UV light. Flash
was achieved by exposure to either I
2
chromatography was performed using silica gel (100–200 mesh),
and the column was usually eluted with an EtOAc/ petroleum ether
1
(
b.p. 60–80 °C) mixture. Melting points are uncorrected. H NMR
–1
ing point. IR (KBr): ν˜ max = 1647, 1459, 1280, 1133, 1000, 914 cm .
13
and C NMR spectroscopic data were recorded with Varian VXR
00 or 400 MHz spectrometers using TMS as the internal standard
and CDCl as the solvent. The coupling constants (J) are given
1
3
H NMR (400 MHz, CDCl ): δ = 1.91–1.98 (m, 4 H), 2.19–2.24
3
(
m, 4 H), 2.93–2.97 (m, 4 H), 5.05–5.10 (m, 4 H), 5.71–5.81 (m, 2
13
3
H) ppm. C NMR (100.6 MHz, CDCl
1
): δ = 21.1, 32.3, 52.1,
3
st
nd
in Hertz (Hz). 1 Generation (A) and 2 Generation (B) Grubbs
catalysts were purchased from Strem and Fluka chemicals, respec-
tively. Allyl bromide and tetrabutylammonium bromide were pur-
chased from the Loba Chemical Company, India, and allyl bromide
was freshly distilled before use. N,NЈ-dimethylformamide was pur-
16.8, 136.4 ppm. HRMS: m/z: (M + 1)+ found 203.1101; calcd.
19 2
for C10H O S 203.1106.
Preparation of Compound 10: A suspension of rongalite (1.41 g,
9.15 mmol), potassium carbonate (1.2 g, 8.69 mmol), tetrabutylam-
monium bromide (29 mg, 0.09 mmol), and 6-bromo-1-hexene 4
(300 mg, 1.84 mmol) in DMF (25 mL) was stirred at room tem-
perature for 72 h and then quenched with cold water (15 mL). The
aqueous phase was extracted with diethyl ether (3×50 mL). The
organic layer was washed with water and brine, dried with anhy-
drous sodium sulfate, and concentrated. The crude compound was
purified by silica gel column chromatography. Elution of the col-
umn with a 10% ethyl acetate/petroleum ether mixture gave the
compound 10 (128 mg, 61%) as a solid having a low melting point.
2 4
chased from Merck. For all the reactions anhydrous Na SO was
used as drying agent after workup. 4-Bromo-1-butene, 5-bromo-1-
pentene and 6-bromo-1-hexene were purchased from Lancaster and
1,8-bis(bromomethyl)naphthalene and 2,2Ј-bis(bromomethyl)-1,1Ј-
biphenyl were purchased from Aldrich. All commercial grade rea-
gents were used without further purification. Infrared spectra were
recorded with a Nicolet 400 FT IR spectrometer in KBr/CH Cl ,
2 2
and the absorptions are reported in cm . The high-resolution mass
measurements were carried out using either a JEOL JMS-DX 303
GC-MS or a Q-Tof Micro (YA-105)-Micromass UK instrument.
–
1
–
1 1
IR (KBr): ν˜ max = 1652, 1479, 1316, 1133, 995, 919 cm . H NMR
400 MHz, CDCl ): δ = 1.51–1.67 (m, 4 H), 1.81–1.92 (m, 4 H),
.08–2.14 (m, 4 H), 2.90–2.97 (m, 4 H), 4.98–5.06 (m, 4 H), 5.72–
(
3
Preparation of Compound 7: A suspension of rongalite (3.85 g,
2
5
3
2
2
5 mmol), potassium carbonate (3.45 g, 25 mmol), tetrabutylam-
monium bromide (80.5 mg, 0.25 mmol), and allyl bromide 1
600 mg, 5 mmol) in DMF (25 mL) was stirred at room tempera-
13
.83 (m, 2 H) ppm. C NMR (100.6 MHz, CDCl
3.2, 52.6, 115.6, 137.6 ppm. HRMS: m/z: (M + 1) found
31.1422; calcd. for C12 S 231.1419.
3
): δ = 21.5, 27.8,
+
(
23 2
H O
ture for 72 h and then quenched with cold water (15 mL). The
aqueous phase was extracted with diethyl ether (3×50 mL). The
organic layer was washed with water and brine, dried with anhy-
drous sodium sulfate, and concentrated. The crude compound was
purified by silica gel column chromatography. Elution of the col-
umn with a 10% ethyl acetate/petroleum ether mixture gave the
diallyl sulfone 7 (184 mg, 50%) as a colorless liquid. IR (neat): ν˜ max
Preparation of Compound 11: A suspension of rongalite (123 mg,
0.80 mmol), potassium carbonate (110 mg, 0.80 mmol), tetrabu-
tylammonium bromide (26 mg, 0.08 mmol), and 1,8-bis(bromome-
thyl)naphthalene 5 (50 mg, 0.16 mmol) in DMF (5 mL) was stirred
at room temperature for 24 h and then quenched with cold water
(15 mL). The aqueous phase was extracted with diethyl ether
): (3×50 mL). The organic layer was washed with water and brine,
dried with anhydrous sodium sulfate, and concentrated. The crude
.2 Hz, 2 H), 5.51–5.53 (d, J = 10 Hz, 2 H), 5.88–5.98 (m, 2 compound was purified by silica gel column chromatography. Elu-
–
1 1
=
1650, 1433, 1321, 1137, 939 cm . H NMR (400 MHz, CDCl
3
δ = 3.70–3.72 (d, J = 8 Hz, 4 H), 5.42–5.46 (dd, J = 16.8, J =
1
13
H) ppm.
C NMR (100.6 MHz, CDCl
3
): δ = 56.1, 125.0,
tion of the column with a 4% ethyl acetate/petroleum ether mixture
+
1
25.1 ppm. HRMS: m/z: (M + 1) found 147.0485; calcd. for
gave the compound 11 (24 mg, 75%) as a colorless solid. M.p.:
C
6
H
11
O
2
S 147.0480.
242 °C (Ref.[ 240–242 °C). H NMR (300 MHz, CDCl
16]
1
3
): δ = 4.57
Eur. J. Org. Chem. 2005, 3581–3585
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 3583

S. Kotha, P. Khedkar, A. K. Ghosh
s, 4 H), 7.30–7.32 (m, 2 H), 7.44–7.49 (m, 2 H), 7.82–7.85 (m, 2 Preparation of Compound 16: To a solution of sulfone 10 (28 mg,
FULL PAPER
(
13
nd
H) ppm. C NMR (75.4 MHz, CDCl
28.0, 129.3, 134.4 ppm.
3
): δ = 55.4, 126.1, 127.1, 0.121 mmol) in dry dichloromethane (5 mL) was added Grubbs 2
1
Generation catalyst B (2 mg, 0.0024 mmol, 2 mol-%), and the reac-
tion mixture was heated to reflux under nitrogen for 4 h. Then, the
reaction mixture was cooled to room temperature and concentrated
to dryness under vacuum. A short pad of silica gel was charged
with the crude reaction mixture and washed with chloroform
Preparation of Compound 12: A suspension of rongalite (115 mg,
.75 mmol), potassium carbonate (103 mg, 0.75 mmol), tetrabu-
0
tylammonium bromide (24 mg, 0.075 mmol), and 2,2Ј-bis(bromo-
methyl)-1,1Ј-biphenyl 6 (50 mg, 0.15 mmol) in DMF (5 mL) was
stirred at room temperature for 24 h and then quenched with cold
water (15 mL). The aqueous phase was extracted with diethyl ether
(
30 mL). The washings were concentrated, and the residue obtained
after the removal of chloroform was rinsed with a small amount of
cold ethyl acetate/petroleum ether mixture (10:1) two to three times
to remove the trace impurities of the catalyst. The colorless solid
(3×50 mL). The organic layer was washed with water and brine,
dried with anhydrous sodium sulfate, and concentrated. The crude
compound was purified by silica gel column chromatography. Elu-
tion of the column with a 4% ethyl acetate/petroleum ether mixture
gave the compound 12 (35 mg, 98%) as a colorless solid. M.p.:
16 obtained (8 mg, 33%) was found to be sparingly soluble in ethyl
acetate but showed good solubility in chloroform and dichloro-
methane. IR (KBr): ν˜ max = 2992, 2944, 1623, 1468, 1309, 1276,
–1
1
1
125, 1142, 1076 cm . H NMR (300 MHz, CDCl
3
): δ = 1.42–1.58
[
17]
1
2
=
CDCl
10–211 °C (Ref.
209–210 °C). H NMR (300 MHz, CDCl
4.03 (s, 4 H), 7.49–7.52 (m, 8 H) ppm. 13C NMR (75.4 MHz,
): δ = 57.4, 128.1, 129.0, 129.4, 129.5, 130.6, 139.9 ppm.
3
): δ
(
m, 8 H), 1.76–1.86 (m, 8 H), 2.06–2.08 (m, 8 H), 2.89–2.98 (m, 8
13
H), 5.30–5.42 (m, 4 H) ppm. C NMR (75.4 MHz, CDCl
3
): δ =
3
2
0.5, 27.5, 31.3, 52.1, 130.6 (major diastereomer) ppm. HRMS:
+
37 4 2
m/z: (M + 1) found 405.2134; calcd. for C20H O S 405.2133.
Preparation of Compound 13: To a solution of sulfone 7 (18 mg,
st
0.123 mmol) in dry dichloromethane (6 mL) was added Grubbs 1
Generation catalyst A (1.97 mg, 0.0024 mmol, 2 mol-%), and the
reaction mixture was heated to reflux under nitrogen for 4 h. Then,
the reaction mixture was cooled to room temperature and concen-
trated to dryness under vacuum. The crude compound was purified
by silica gel column chromatography. Elution of the column with
a 15% ethyl acetate/petroleum ether mixture gave the 2,5-dihydro-
thiophene 1,1-dioxide (13) (14 mg, 97%) as a colorless crystalline
solid. M.p.: 63–64 °C (Ref.[ 64–65.5 °C). 1H NMR (400 MHz,
Acknowledgments
We gratefully acknowledge the CSIR and DST (NST) for financial
support. PK and AKG thank CSIR, New Delhi and IIT-Bombay
respectively for the award of Research Fellowships. We would like
to acknowledge RSIC-Mumbai for providing the spectroscopic
data.
18]
CDCl
3
): δ = 3.76 (s, 4 H), 6.08 (s, 2 H) ppm.
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0
1
.402 mmol) in dry dichloromethane (10 mL) was added Grubbs
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st
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(
1
2
KBr): ν˜ max = 3037, 2972, 1688, 1455, 1341, 1313, 1276, 1211, 1199,
–1 1
3
109 cm . H NMR (300 MHz, CDCl ): δ = 2.48–2.54 (m, 4 H),
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69.0292; calcd. for C H O SNa 169.0299.
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0.123 mmol) in dry dichloromethane (5 mL) was added Grubbs 2
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tion mixture was heated to reflux under nitrogen for 4 h. Then, the
reaction mixture was cooled to room temperature and concentrated
to dryness. A short pad of silica gel was charged with the crude
reaction mixture and washed with chloroform (30 mL). The wash-
ings were concentrated, and the residue obtained after the removal
of chloroform was rinsed with a small amount of cold ethyl acetate/
petroleum ether mixture (10:1) two to three times to remove trace
impurities of the catalyst. The colorless solid 15 obtained (13 mg,
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3
good solubility in chloroform and dichloromethane. IR (KBr): ν˜ max
–
1 1
=
3001, 2923, 1651, 1455, 1305, 1288, 1248, 1133, 1113 cm . H
NMR (300 MHz, CDCl ): δ = 1.85–1.95 (m, 8 H), 2.00–2.25 (m, 8
H), 2.86–2.98 (m, 8 H), 5.05–5.48 (m, 4 H) ppm. 1 C NMR
75.4 MHz, CDCl ): δ = 21.3, 30.5, 51.2, 130.7 (major dia-
stereomer) ppm. HRMS: m/z: (M + 1) found 349.1506; calcd. for
349.1507.
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C H O S
3584
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 3581–3585

Synthesis of Symmetrical Sulfones from Rongalite: Expansion to Cyclic Sulfones
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FULL PAPER
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Received: April 14, 2005
Published Online: June 30, 2005
Eur. J. Org. Chem. 2005, 3581–3585
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