o-benzenedisulfonimide: A novel and reusable catalyst for acid-catalyzed organic reactions

Article abstract of DOI:10.1055/s-2007-985559

The o-benzenedisulfonimide is used as Br?nsted acid in catalytic amounts in various acid-catalyzed organic reactions, such as etherification, esterification, and acetalization; the conditions required are mild and in the considered examples the results are always good. A useful aspect of the use of this catalyst is its easy recovery in high yield from the reaction mixture and its reuse in other reactions, with economic and ecological advantages. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-985559

LETTER
2209
o-Benzenedisulfonimide: A Novel and Reusable Catalyst for Acid-Catalyzed
Organic Reactions
o
-Benzenedisulfonimid
a
e
–
Catalys
r
t
for
A
c
g
id-Catalyzed
h
O
rganic Re
ections rita Barbero,* Silvano Cadamuro, Stefano Dughera, Paolo Venturello
Dipartimento di Chimica Generale ed Organica Applicata dell’Università, Via Pietro Giuria, 7, 10125 Torino, Italy
Fax +39(011)6707642; E-mail: margherita.barbero@unito.it
Received 8 June 2007
Initially, to confirm this hypothesis, we reacted the allylic
Abstract: The o-benzenedisulfonimide is used as Brønsted acid in
catalytic amounts in various acid-catalyzed organic reactions, such
as etherification, esterification, and acetalization; the conditions re-
quired are mild and in the considered examples the results are al-
alcohol 1,3-diphenylprop-2-en-1-ol (3) in EtOH, in the
presence of Pd(OAc)2 as precatalyst, but surprisingly we
did not observe the formation of the corresponding ethoxy
ways good. A useful aspect of the use of this catalyst is its easy derivative. Instead, the reaction occurred in the absence of
recovery in high yield from the reaction mixture and its reuse in
other reactions, with economic and ecological advantages.
the metal catalyst, but in the presence of catalytic amounts
of 1.
Key words: o-Benzenedisulfonimide, Brønsted acid, acid-cata-
The high acidity of this Brønsted acid is known,12 but to
lyzed organic reactions, reusable catalyst, dehydrative reactions
the best of our knowledge, for the first time this strong
acid is shown to effect a dehydration of an alcohol, name-
ly the allylic alcohol 3, to give in ethanol the isolated ethyl
ether. As a consequence, we decided to evaluate the syn-
The o-benzenedisulfonimide (1) was first reported in
1921 and 1926 by Holleman1 and by Hurtley and Smiles,2
thetic potential of the imide 1 as a novel Brønsted acid cat-
respectively, and more recently by Hendrickson,3
alyst in some acid-catalyzed reactions, frequently used in
Blaschette,4 Davis,5 and their co-workers. The key inter-
organic synthesis to introduce useful protecting groups.
mediate is the o-benzenedisulfonyl chloride, which can be
A further valuable aspect of the use of 1 is its easy re-
prepared starting from the commercially available o-ben-
covery in high yield from the reaction mixture, due to its
complete solubility in water, and its reuse without loss of
catalytic activity in other reactions, with economic and
ecological advantages.
zenedisulfonic acid dipotassium salt,2,5 anthranilic acid,6
o-aminobenzenesulfonic acid,7 and o-bis(methylthio)ben-
zene;8 now it is also commercially available by many
suppliers.
In this paper we describe our preliminary results obtained
in some explorative acid-catalyzed reactions,13 carried out
in the presence of catalytic amounts of 1 (Scheme 1).
In the last decade, we reported our results on the synthetic
applications of the N-hydroxy derivative of 1 and of its
conjugate base as stabilizing counterion for arenediazoni-
um o-benzenedisulfonimides, a new family of arenedi-
azonium salts, exceptionally stable in the dry state and
therefore good synthesis intermediates both in aqueous
and in anhydrous conditions.9
OR1
Ph
OH
R1OH, cat.
Ph
Ph
Ph
Ph
(solvent)
3
4a−d
Recently, in the course of our investigations concerning
the reactivity of these salts in metal-catalyzed cross-cou-
pling reactions,10 we studied the Heck-type arylation of
allylic alcohols.10c Along with the expected mixtures of
b- and a-arylated carbonyl compounds and of arylated
allylic alcohols, in some cases we isolated the ethoxy
derivatives 2 (Figure 1), whose formation was ascribed to
a Tsuji–Trost reaction of the solvent ethanol on the inter-
mediate arylated allylic alcohol.11
O
O
R1OH, cat.
(solvent)
Ph
OR1
OH
5
6a,b
OR1
O
R1OH, cat.
(solvent)
R
OR1
8a−d
R
7a−c
SO2
NH
SO2
cat. =
OEt
1
R1
R2
2
Scheme 1
Figure 1
Etherification, esterification, and acetalization were cho-
sen in view of the synthetic significance and simplicity of
the dehydrative acid-catalyzed methods of synthesis.14–16
SYNLETT 2007, No. 14, pp 2209–2212
0
3
.0
9
.2
0
0
7
Advanced online publication: 24.07.2007
DOI: 10.1055/s-2007-985559; Art ID: G18207ST
© Georg Thieme Verlag Stuttgart · New York

2210
M. Barbero et al.
LETTER
In Table 1 we report detailed descriptions of the examined The preferred catalytic amount of o-benzenedisulfon-
reactions (reactants, molar ratio, reaction conditions) and imide (1) was 5% mol (increasing amount gave yields
results (yields of pure isolated products by flash chroma- slightly better; entries 1–3, values in parentheses).17
tography).
Direct dehydrative esterification of phenylacetic acid (5)
All the considered reactions were conducted in an open- with primary aliphatic alcohols was achieved in high
air flask, using analytical grade reagents and solvents; yields and purity, by carrying out the reaction in toluene
water is the only side product.
at 90 °C, with the reagents in almost equimolar amounts
and in the presence of 20–25% mol of o-benzenedisulfon-
imide (1).18
The etherification of 1,3-diphenylprop-2-en-1-ol (3) with
primary or secondary alcohols (entries 1–4) occurred in
very mild conditions (r.t. or 60 °C) and high yields. The Finally, to further explore the synthetic usefulness of the
reaction was carried out in excess of aliphatic alcohol as o-benzenedisulfonimide as acid catalyst, we prepared
solvent (entries 1 and 2) or in etherate solvent with the al- some dimethyl acetals in mild reaction conditions (at r.t.
cohols in stoichiometric amounts or in slight excess (THF; and in air) and short times. Good conversions were ob-
entries 3 and 4). In the course of the reactions we observed tained for the aromatic aldehyde 7a (entry 7), the conju-
the exclusive formation of the mixed ethers 4a–d; no gated cinnamic aldehyde (7b, entry 8), and the acid-
traces were detected or isolated of the symmetric ethers. sensitive aldehyde 7c (entry 9). The acetal formation was
Table 1 o-Benzenedisulfonimide-Catalyzed Etherification, Esterification, and Acetalization Reactions
Entry Reactants
Reactants
(molar
ratio)
1
Solvent
Temp
(°C)
Time
(min)
Products 4, 6, 8
Yield
(%)a,b
(mol%)
3, 5, 7
R1OH
EtOH
1
5
5
5
5
EtOH
r.t.
r.t.
r.t.
120
15
77 (81)c
74 (77)c
85 (90)c
70
OEt
OH
Ph
Ph
Ph
Ph
4a
3
2
3
4
3
3
3
i-PrOH
BnOH
BuOH
i-PrOH
THF
Oi-Pr
Ph
OBn
Ph
4b
1:1
1:2
60
Ph
Ph
4c
THF
Reflux 150
On-Bu
Ph
Ph
4d
5
6
7
8
9
PhCH2COOH
5
BuOH
1:1.1
1:1
25
PhMe
PhMe
MeOH
MeOH
MeOH
90
90
r.t.
r.t.
r.t.
90
90
10
10
10
PhCH2COOn-Bu
6a
90
5
n-C8H17OH
MeOH
20
PhCH2COOn-C8H17
6b
85
4-ClC6H4CHO
7a
0.5
0.5
0.5
4-ClC6H4CH(OMe)2
8a
85 (90)d
64 (72)d,e
64 (65)d,e
PhCH=CHCHO
7b
MeOH
PhCH=CHCH(OMe)2
8b
MeOH
CHO
S
CH(OMe)2
S
7c
7a
8c
10
HOCH2CH2OH 1:3
1
PhMe
90
60
87e
O
9
O
Cl
8d
a Yields refer to pure isolated products (flash chromatography).
b Products were characterized by GC-MS, 1H NMR, and 13C NMR spectra and by comparison with known or authentic commercial compounds.
c In parentheses yield of product obtained in the presence of 1 10% mol.
d In parentheses yield of product obtained in the presence of 1 1% mol.
e Unreacted carbonyl compound 7 was recovered (entry 8: 7b, 23%; entry 9: 7c, 5%; entry 10: 7a, 11%).
Synlett 2007, No. 14, 2209–2212 © Thieme Stuttgart · New York

LETTER
o-Benzenedisulfonimide – Catalyst for Acid-Catalyzed Organic Reactions
2211
(9) (a) Barbero, M.; Degani, I.; Fochi, R.; Perracino, P. WO
9839312, 1998; Chem. Abstr. 1998, 129, 244942.
also achieved in solvent (molar ratio 7a:ethane-1,2-diol
(9) = 1:3, in toluene at 90 °C; entry 10). The optimal cat-
alytic amount of catalyst 1 was 0.5–1% mol, neutralized
at the end of the reaction by addition of solid NaHCO3;
pure acetals were isolated by flash chromatography on
silica gel deactivated by Et3N.19
(b) Barbero, M.; Crisma, M.; Degani, I.; Fochi, R.;
Perracino, P. Synthesis 1998, 1171. (c) Barbero, M.;
Degani, I.; Dughera, S.; Fochi, R. Synthesis 2004, 2386; and
references cited therein.
(10) (a) Artuso, E.; Barbero, M.; Degani, I.; Dughera, S.; Fochi,
R. Tetrahedron 2006, 62, 3146. (b) Dughera, S. Synthesis
2006, 1117. (c) Barbero, M.; Cadamuro, S.; Dughera, S.
Synthesis 2006, 3443. (d) Barbero, M.; Cadamuro, S.;
Dughera, S.; Giaveno, C. Eur. J. Org. Chem. 2006, 4884.
(11) Tsuji, J. Palladium Reagents and Catalysts: New
Perspectives for the 21st Century; Wiley: Chichester, 2004,
Chap. 4, 431–469; and references therein.
From all the reactions, after the workup of the reaction
mixture, o-benzenedisulfonimide (1) was recovered in
high yield, recyclable as catalyst for other reactions.20
Amongst the examples reported in Table 1 and taking into
consideration only Brønsted acid catalyzed dehydrative
syntheses, ether 4c was prepared in 77% yield from the
starting alcohols in the presence of Ir complex activated
by H2 molecule;21 esters 6a and 6b were prepared from
acid 5 and the corresponding alcohols in comparable
yields by prolonged heating at higher temperatures;22 ace-
tals 8a,b,d were obtained directly from the corresponding
aldehydes and alcohols in comparable yields, but after
longer reaction times.23
(12) King, J. F. In The Chemistry of Sulphonic Acids, Esters and
their Derivatives; Patai, S., Ed.; John Wiley: New York,
1991, Chap. 6, 249–259.
(13) For recent works on acid-catalyzed dehydrative
etherification, esterification, and acetalization reactions with
metal catalysts, see for example: (a) Sharma, G. V. M.;
Mahalingam, A. K. J. Org. Chem. 1999, 64, 8943.
(b) Sharma, G. V. M.; Prasad, T. R.; Mahalingam, A. K.
Tetrahedron Lett. 2001, 42, 759. (c) Saburi, H.; Tanaka, S.;
Kitamura, M. Angew. Chem. Int. Ed. 2005, 44, 1730.
(d) Shibata, T.; Fujiwara, R.; Ueno, Y. Synlett 2005, 152.
With solid-acid catalysis: (e) Scott, L. T.; Naples, J. O.
Synthesis 1973, 209. (f) Olah, G. A.; Shamma, T.; Prakash,
G. K. S. Catal. Lett. 1997, 46, 1. (g) Harmer, M. A.; Sun, Q.
Appl. Catal., A 2001, 221, 45. (h) Shen, J. G. C.; Herman, R.
G.; Klier, K. J. Phys. Chem. B 2002, 106, 9975. (i) Sanz,
R.; Martinez, A.; Miguel, D.; Alvarez-Gutierrez, J. M.;
Rodriguez, F. Adv. Synth. Catal. 2006, 348, 1841. In
supercritical fluids: (j) Gray, W. K.; Smail, F. R.; Hitzler, M.
G.; Ross, S. K.; Poliakoff, M. J. Am. Chem. Soc. 1999, 121,
10711. In ionic liquids: (k) Cole, A. C.; Jensen, J. L.; Ntai,
I.; Tran, K. L. T.; Weaver, K. J.; Forbes, D. C.; Davis, J. H.
Jr. J. Am. Chem. Soc. 2002, 124, 5962. (l) Davis, J. H. Jr.
WO 03086605, 2003; Chem. Abstr. 2003, 139, 325782 . In
water: (m) Manabe, K.; Iimura, S.; Sun, X.-M.; Kobayashi,
S. J. Am. Chem. Soc. 2002, 124, 11971.
The advantages of the proposed methodology are mild re-
action conditions, short reaction times, and no formation
of side products. Compared to strong liquid or solid
Brønsted acids, extensively used from research laborato-
ries to chemical manufacturing plants, the here proposed
catalyst turns out to be a nontoxic, nonvolatile and non-
corrosive chemical product, easily recoverable from the
reaction mixture without need of binding to solid matrix.
A thorough study on its wider use in organic transforma-
tions is in progress.
In this communication, we reported the synthetic applica-
bility of the o-benzenedisulfonimide as a novel acid cata-
lyst for acid-catalyzed organic reactions, in view of the
continuous interest in new methods of homogeneous
catalysis, environmentally friendly, and economically
sustainable.
(14) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 3rd ed.; Wiley: New York, 1999, Chap.
2, 17–245. (b) Feuer, H.; Hooz, J. In The Chemistry of the
Ether Linkage; Patai, S., Ed.; Interscience: New York, 1967,
Chap. 10, 445–498. (c) Meerwein, H. In Methoden der
Organischen Chemie (Houben–Weyl), Vol. VI/3; Thieme
Verlag: Stuttgart, 1965, 7–140.
Acknowledgment
This work was supported by Italian MIUR and by the Università
degli Studi di Torino.
(15) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 3rd ed.; Wiley: New York, 1999, Chap.
5, 369–453. (b) Euranto, E. K. In The Chemistry of
Carboxylic Acids and Esters; Patai, S., Ed.; Interscience:
New York, 1969, Chap. 11, 505–588.
(16) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 3rd ed.; Wiley: New York, 1999, Chap.
4, 293–368. (b) Schmitz, E.; Eichhorn, I. In The Chemistry
of the Ether Linkage; Patai, S., Ed.; Interscience: New York,
1967, Chap. 7, 310–351. (c) Bergstrom, R. G. In The
Chemistry of Ethers, Crown Ethers, Hydroxyl Groups and
Their Sulphur Analogues, Suppl. E, Part 2; Wiley:
Chichester, 1980, Chap. 20, 881–902. (d) Shimizu, K.-I.;
Hayashi, E.; Hatamachi, T.; Kodama, T.; Kitayama, Y.
Tetrahedron Lett. 2004, 45, 5135. (e) Kumar, R.; Kumar,
D.; Chakraborti, A. K. Synthesis 2007, 299.
References and Notes
(1) Hollemann, A. F. Recl. Trav. Chim. Pays-Bas 1921, 40, 446.
(2) Hurtley, W. R.; Smiles, S. J. Chem. Soc. 1926, 1821.
(3) Hendrickson, J. B.; Okano, S.; Bloom, R. K. J. Org. Chem.
1969, 34, 3434.
(4) Blaschette, A.; Jones, P. G.; Hamann, T.; Näveke, M.
Z. Anorg. Allg. Chem. 1993, 619, 912.
(5) Davis, F. A.; Sundarababu, G.; Qi, H. Org. Prep. Proced.
Int. 1998, 30, 107.
(6) Barbero, M.; Degani, I.; Fochi, R.; Regondi, V. Gazz. Chim.
Ital. 1986, 116, 165.
(7) Sørbye, K.; Tautermann, C.; Carlsen, P.; Fiksdahl, A.
Tetrahedron: Asymmetry 1998, 9, 681.
(8) Karino, H.; Goda, H.; Sakamoto, J.-I.; Yoshida, K.;
Nishiguchi, H. WO 9633167, 1996; Chem. Abstr. 1997, 126,
18657.
Synlett 2007, No. 14, 2209–2212 © Thieme Stuttgart · New York

2212
M. Barbero et al.
LETTER
(17) Typical Procedure for o-Benzenedisulfonimide-
Catalyzed Etherification (Entry 1, Table 1)
0.02 mmol) and the reaction mixture was stirred at 90 °C for
60 min. The reaction mixture was treated with solid
NaHCO3, evaporated under reduced pressure, and the
residue was poured into Et2O–H2O (40 mL, 1:1). The
aqueous layer was separated. The organic extract was dried
over Na2SO4, and evaporated under reduced pressure; the
crude residue was chromatographed on a short column (PE–
Et2O, 9.5:0.5) to provide pure 4-chlorobenzaldehyde
ethlylene acetal in 87% yield (8d; 0.32 g); colorless oil with
spectral data identical to those reported.19b 1H NMR: d =
3.92–3.99 (m, 2 H), 4.02–4.09 (m, 2 H), 5.72 (s, 1 H), 7.29
(d, J = 8.8 Hz, 2 H), 7.36 (d, J = 8.6 Hz, 2 H). 13C NMR: d =
65.51 (2 C), 103.21, 128.10 (2 C), 128.75 (2 C), 135.20,
136.69. MS (EI, 70 eV): m/z (%) = 184 (35) [M+], 183 (100).
(b) Katritzky, A. R.; Odens, H. H.; Voronkov, M. V. J. Org.
Chem. 2000, 65, 1886.
To a solution of 1,3-diphenylprop-2-en-1-ol (3; 0.42 g, 2.0
mmol) in abs. EtOH (10 mL) was added o-benzenedisulfon-
imide (1; 5 mol%; 0.02 g, 0.1 mmol); the reaction mixture
was stirred at r.t. The reaction was monitored by TLC
(PE–Et2O, 6:4), GC, and GC-MS analyses until complete
disappearance of the starting material. Then the reaction
mixture was evaporated under reduced pressure and the
residue was poured into Et2O–H2O (40 mL, 1:1). The
aqueous layer was separated. The organic extract was
washed with H2O (20 mL), dried over Na2SO4, and
evaporated under reduced pressure. The crude residue was
chromatographed on a short column (PE–Et2O, 6:4) to
provide pure (E)-1,3-diphenyl-3-ethoxyprop-1-ene (4a; GC,
GC-MS, TLC, 1H NMR) in 77% yield (0.37 g); colorless oil.
1H NMR: d = 1.33 (t, J = 7.0 Hz, 3 H), 3.60 (superimposed
q, J = 7.0 Hz, 2 H diastereotopic), 4.98 (d, J = 6.8 Hz, 1 H),
6.38 (dd, J = 16.0, 6.8 Hz, 1 H), 6.68 (d, J = 16.0 Hz, 1 H),
7.25–7.50 (m, 10 H). 13C NMR: d = 15.72, 64.33, 82.86,
126.93 (2 C), 127.17 (2 C), 127.94, 128.00, 128.84 (4 C),
131.00, 131.45, 136.97, 141.86. MS (EI, 70 eV): m/z (%)
238 (70) [M+], 105 (100).
(20) The aqueous layer and aqueous washing from the various
reactions were collected and evaporated under reduced
pressure. The residue was passed through a column of
Dowex 50X8 ion-exchange resin (1.6 g for 1 g of product),
eluting with H2O (about 35 mL). After removal of H2O
under reduced pressure, virtually pure (1H NMR) o-
benzenedisulfonimide(1) was recovered; mp 192–194 °C,
from toluene (lit. 3: mp 192–194 °C).
(21) Matsuda, I.; Wakamatsu, S.; Komori, K.-I.; Makino, T.;
Itoh, K. Tetrahedron Lett. 2002, 43, 1043.
(22) For compound 6a, see: (a) Sharghi, H.; Sarvari, M. H.;
Eskandari, R. J. Chem. Res., Synop. 2005, 488.
(18) Typical Procedure for o-Benzenedisulfonimide-
Catalyzed Esterification (Entry 5, Table 1)
To a solution of phenylacetic acid (5; 0.27 g, 2.0 mmol) and
butan-1-ol (0.16 g, 2.2 mmol) in toluene (10 mL) was added
o-benzenedisulfonimide (1; 25 mol%; 0.11 g, 0.5 mmol) and
the reaction mixture was stirred at 90 °C for 30 min. After
the usual workup, the crude residue was chromatographed
on a short column (PE–Et2O, 8:2) to provide pure butyl
phenylacetate (6a; GC, GC-MS, TLC, 1H NMR) in 90%
yield (0.38 g); colorless oil with spectral data identical to
those reported.22d 1H NMR: d = 0.85 (t, J = 7.0 Hz, 3 H),
1.23–1.34 (m, 2 H), 1.48–1.58 (m, 2 H), 3.56 (s, 2 H), 4.04
(t, J = 6.6 Hz, 2 H), 7.15–7.28 (m, 5 H). 13C NMR: d = 13.86,
19.27, 30.80, 41.66, 64.94, 127.21, 128.72 (2 C), 129.43 (2
C), 134.40, 171.88; MS (EI, 70 eV): m/z (%) = 192 (5) [M+],
91 (100).
(b) Vijayakumar, B.; Iyengar, P.; Nagendrappa, G.; Prakash,
B. S. J. J. Indian Chem. Soc. 2005, 82, 922. (c) Banerjee,
A.; Sengupta, S.; Adak, M. M.; Banerjee, G. C. J. Org.
Chem. 1983, 48, 3106. (d) For compounds 6a and 6b, see:
Gumaste, V. K.; Deshmukh, A. R. A. S.; Bhawal, B. M.
Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.
1996, 35, 1174.
(23) For compounds 8a and 8b, see: (a) Shimizu, K.-I.; Hayashi,
E.; Hatamachi, T.; Kodama, T.; Kitayama, Y. Tetrahedron
Lett. 2004, 45, 5135. For compound 8d, see: (b) Azzena,
U.; Dettori, G.; Sforazzini, G.; Yus, M.; Foubelo, F.
Tetrahedron 2006, 62, 1557. (c) Shimizu, K.-I.; Hayashi,
E.; Hatamachi, T.; Kodama, T.; Higuchi, T.; Satsuma, A.;
Kitayama, Y. J. Catal. 2005, 231, 131. (d) Huerta, F. F.;
Gomez, C.; Yus, M. Tetrahedron 1999, 55, 4043.
(19) (a) Typical Procedure for o-Benzenedisulfonimide-
Catalyzed Acetalization (Entry 10, Table 1)
To a solution of 4-chlorobenzaldehyde (7a; 0.28 g, 2 mmol)
and ethane-1,2-diol (9; 0.37 g, 6 mmol) in toluene (5 mL)
was added o-benzenedisulfonimide (1; 1 mol%; 0.0044 g,
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