4
Tetrahedron Letters
According to the proposed mechanism, molecular iodine is CHCl3 than aqueous media, CH3CN, and PEG-200, possibly
reduced to non-solvated hydrogen iodide by the reaction with due to the lack of solvation of the in situ generated HI.
NaHSO3 and trace amounts of H2O in the CHCl3.
In summary, we have reported molecular iodine as a highly
Consequently, hydrogen iodide reduces the sulfoxide
efficient catalyst for the reduction of various sulfoxides using
functionality to the sulfide via (i) protonation of the sulfoxide
NaHSO3. This method has advantages such as high yields,
oxygen functionality followed by iodide attack of the sulfur
mild reaction conditions, a simple experimental procedure, and
atom, (ii) protonation of the hydroxy group followed by iodide
use of an inexpensive commercially available catalyst and
attack on the iodine atom linked to the sulfur atom. The
reagent.
reduction by hydrogen iodide proceeds more efficiently in
13. Garcia, N.; Garcia-Garcia, P.; Fernandez-Rodriguez, M.A.; Rubio,
Acknowledgments
We are thankful to the Persian Gulf University Research
R.; Pedrosa, M.R.; Arnaiz, F.J.; Sanz, R. Adv. Synth. Catal. 2012,
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5.
22. General Procedure: A mixture of a sulfoxide (1 mmol), NaHSO3
(1.1 mmol), and I2 (0.025-0.1 mmol) in CHCl3 (1 mL) was stirred
at room temperature or at 50 °C. The progress of the reaction was
monitored by TLC. After completion, the solution was decanted
from the residue, washed with EtOAc (2 × 1 mL). The combined
organic layers were concentrated and the residue purified by
chromatography on silica gel using n-hexane as eluent.
Benzyl(phenyl)sulfide (Table 2, entry 4): Colorless oil; 1HNMR
(250 MHz, CDCl3): δ 7.37-7.18 (m, 10H), 4.17 (s, 2H); 13CNMR
(62.5 MHz, CDCl3): δ 137.5, 136.4, 129.8, 128.9, 128.6, 127.2,
126.4, 39.0. Anal. calcd for C13H12S: C, 77.95; H, 6.04; S, 16.01.
Found: C, 78.09; H, 6.11; S, 15.80. Butyl(4-methoxyphenyl)sulfide
6.
7.
8.
9.
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1
(Table 2, entry 10): Colorless oil; HNMR (250 MHz, CDCl3): δ
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7.34 (d, J = 9.0 Hz, 2H), 6.84 (d, J = 9.0, 2H), 3.87 (s, 3H), 2.82
(t, J = 7.1 Hz, 2H), 1.63-1.52 (m, 2H), 1.49-1.37 (m, 2H), 0.90 (t,
J = 7.3 Hz, 3H); 13CNMR (62.5 MHz, CDCl3): δ 158.7, 132.9,
126.9, 114.5, 55.3, 35.5, 31.5, 21.8, 13.7. Anal. calcd for
C11H16OS: C, 67.30; H, 8.22; S, 16.33. Found: C, 67.45; H, 8.15;
S, 16.43. Allyl(benzyl)sulfide (Table 2, entry 14): Colorless oil;
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