2776
K. Bahrami et al.
LETTER
(6) Blotny, G. Tetrahedron Lett. 2003, 44, 1499.
(7) Meinzer, A.; Breckel, A.; Thaher, B. A.; Manicone, N.; Otto,
H.-H. Helv. Chim. Acta 2004, 87, 90.
(8) Nishiguchi, A.; Maeda, K.; Miki, S. Synthesis 2006, 4131.
(9) Prakash, G. K. S.; Mathew, T.; Panja, C.; Olah, G. A. J. Org.
Chem. 2007, 72, 5847.
dergoes rapid isomerization to the thiosulfonate 7. The
latter sulfonate can then easily furnish sulfonyl chloride 3.
Conversion of 6 into 7 has been well recognized and doc-
umented.12
In conclusion, H2O2/ZrCl4 is an extremely efficient re-
agent system for the conversion of thiols and disulfides
into sulfonyl chlorides.13 The advantages are excellent
yields, extremely fast reaction, low cost, and room tem-
perature conditions. This methodology also overcomes
the problem of unwanted by-product formation. We be-
lieve that the present approach could lead to new possibil-
ities for medicinal chemistry and material sciences and
could be an important addition to the existing methodolo-
gies.
(10) Zhang, Z.-H.; Li, T.-S. Curr. Org. Chem. 2009, 13, 1.
(11) (a) Bahrami, K. Tetrahedron Lett. 2006, 47, 2009.
(b) Khodaei, M. M.; Bahrami, K.; Khedri, M. Can. J. Chem.
2007, 85, 7. (c) Khodaei, M. M.; Bahrami, K.; Karimi, A.
Synthesis 2008, 1682. (d) Bahrami, K.; Khodaei, M. M.;
Kavianinia, I. Synthesis 2007, 547. (e) Bahrami, K.;
Khodaei, M. M.; Naali, F. J. Org. Chem. 2008, 73, 6835.
(f) Bahrami, K.; Khodaei, M. M.; Naali, F. Synlett 2009,
569. (g) Bahrami, K.; Khodaei, M. M.; Tirandaz, Y.
Synthesis 2009, 369.
(12) (a) Freeman, F. Chem. Rev. 1984, 84, 117. (b) Oae, S.;Kim,
Y. H.; Takara, T.; Fukushima, D. Tetrahedron Lett. 1977,
18, 1195. (c) Oae, S.; Takara, T.; Kim, Y. H. Bull. Chem.
Soc. Jpn. 1982, 55, 2484. (d) Oae, S.; Shinhama, K.;
Fujimori, K.; Kim, Y. H. Bull. Chem. Soc. Jpn. 1980, 53,
775. (e) Chau, M. M.; Kice, J. L. J. Am. Chem. Soc. 1976, 98,
7711.
Acknowledgment
We are thankful to the Razi University Research Council for partial
support of this work.
(13) Zirconium tetrachloride, hydrogen peroxide (30%) as well
as all the thiol derivatives employed as substrates are
commercial products (Merck chemical company) and were
used without further purification. Disulfides were prepared
according to our previously reported procedure.14
Melting points were determined in a capillary tube and are
uncorrected. 1H NMR and 13C NMR spectra were recorded
on a Bruker-200 NMR spectrometer using TMS as internal
standard. The concentration of the commercial 30% H2O2
solution was checked iodometrically prior to use.
Synthesis of Sulfonyl Chlorides; General Procedure:
A mixture of thiol (1 mmol), 30% H2O2 (3 mmol, 0.3 mL)
and ZrCl4 (1 mmol, 0.233 g) was stirred in MeCN (5 mL) at
25 °C for the appropriate time. After completion of the
reaction as indicated by TLC, the reaction mixture was
quenched by adding H2O (10 mL), and extracted with
EtOAc (4 × 5 mL). The extract was dried with anhydrous
MgSO4 and the filtrate was evaporated under vacuum to
afford the analytically pure product (Table 2). An identical
procedure was employed using 30% H2O2 (2 mmol, 0.2 mL)
and ZrCl4 (1 mmol, 0.233 g) for the oxidative chlorination of
disulfides (Table 3).
References and Notes
(1) Carey, F. A. Organic Chemistry, 2nd ed.; McGraw-Hill,
Inc.: New York, 1992.
(2) Stadtman, E. R. Science 1992, 257, 1220.
(3) (a) Hoyle, J. The Chemistry of Sulfonic Acids, Esters and
their Derivatives, In The Chemistry of Functional Groups;
Patai, S.; Rapport, Z., Eds.; John Wiley & Sons: New York,
1991, Chap. 10, 351. (b) Tanaka, K. The Chemistry of
Sulfonic Acids, Esters and their Derivatives, In The
Chemistry of Functional Groups; Patai, S.; Rapport, Z.,
Eds.; John Wiley & Sons: New York, 1991, Chap. 11, 401.
(c) Moore, J. D.; Herpel, R. H.; Lichtsinn, J. R.; Flynn, D. L.;
Hanson, P. R. Org. Lett. 2003, 5, 105. (d) Dubbaka, S. R.;
Vogel, P. J. Am. Chem. Soc. 2003, 125, 15292. (e) Kværnø,
L.; Werder, M.; Hauser, H.; Carreira, E. M. Org. Lett. 2005,
7, 1145. (f) Lassalle, G.; Galtier, D.; Galli, F. European
patent 643047, 1995. (g) Lezina, O. M.; Kuchin, A. V.;
Rubtsova, S. A. Russian patent 2289574, 2006.
(4) (a) Watson, R. J.; Batty, D.; Baxter, A. D.; Hannah, D. R.;
Owen, D. A.; Montana, J. G. Tetrahedron Lett. 2002, 43,
683. (b) Percec, V.; Bera, T. K.; De B, B.; Sanai, Y.; Smith,
J.; Holerca, M. N.; Barboiu, B.; Grubbs, B. B. B.; Fréchet,
J. M. J. J. Org. Chem. 2001, 66, 2104. (c) Chen, Z.;
Demuth, T. P. Jr.; Wireko, F. C. Bioorg. Med. Chem. Lett.
2002, 11, 2111.
All of the products are known compounds and were easily
characterized by comparison with authentic samples (1H
NMR, 13C NMR, mp).
(14) Mohammadpoor-Baltork, I.; Memarian, H. R.; Bahrami, K.
Phosphorus, Sulfur, and Silicon 2004, 179, 2315.
(5) Gareau, Y.; Pellicelli, J.; Laliberté, S.; Gauvreau, D.
Tetrahedron Lett. 2003, 44, 7821.
Synlett 2009, No. 17, 2773–2776 © Thieme Stuttgart · New York