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Scheme 4 Plausible reaction pathway
produced in situ from copper powder(0) in Na2S solution, is
considered to be the active copper species involved in this
coupling reaction.
In summary, using copper powder as catalyst and Na2S
as ultimate thiol source, a highly effective and direct meth-
od for the preparation of aryl thiols from aryl iodides was
developed. Preliminary study for reaction pathway suggest-
ed that 1,2-ethanedithiol functioned as catalytic reagents
and was indispensable for the production of aryl thiols in
high yields. A broad range of aryl thiols were readily ob-
tained from aryl iodides when treated with our developed
conditions. The efficiency and economy allowed our proto-
col to be a promising method for further application in both
laboratory and industry.
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Funding Information
(18) Palani, T.; Park, K.; Song, K.-H.; Lee, S. Adv. Synth. Catal. 2013,
355, 1160.
(19) Liu, Y.; Kim, J.; Seo, H.; Park, S.; Chae, J. Adv. Synth. Catal. 2015,
357, 2205.
(20) (a) Zhao, D.-B.; Wu, N.-J.; Zhang, S.; Xi, P.-H.; Su, X.-Y.; Lan, J.-B.;
You, J.-S. Angew. Chem. Int. Ed. 2009, 48, 8729. (b) Tlili, A.; Xia,
N.; Monnier, F.; Taillefer, M. Angew. Chem. Int. Ed. 2009, 48,
8725. (c) Maurer, S.; Liu, W.; Zhang, X.-J.; Jiang, Y.-W.; Ma, D.-W.
Synlett 2010, 976. (d) Kim, J.; Battsengel, O.; Liu, Y.; Chae, J. Bull.
Korean Chem. Soc. 2015, 36, 2833.
We gratefully acknowledge the financial support by the Fundamental
Research Funds for the Central Universities (DUT15RC(3)043;
DUT17LK23), National Research Foundation of Korea (Basic Science
Research Program Fund: NRF2015R1D1A1A01060188).
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(21) General Experimental Procedure for the Synthesis of Aryl
Thiols from Aryl Iodides
To a test tube containing a magnetic bar was added aryl iodide
(1 mmol), copper powder (6.35 mg, 0.1 mmol), Na2S·9H2O
(720.54 mg, 3 mmol), and DMSO (2 mL). After flushing with
argon, 1,2-ethanedithiol (8.4 μL, 0.1 mmol) was added. The
mixture was stirred in the oil bath at 100 °C for 20 h. After
cooled to ambient temperature, the reaction mixture was dis-
tributed in aq HCl (5%) and EtOAc. The organic layer was sepa-
References and Notes
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39, 1355. (b) Hand, C. E.; Honek, J. F. J. Nat. Prod. 2005, 68, 293.
(c) Roy, K.-M. Thiols and Organic Sulfides, In Ullmann’s Encyclo-
pedia of Industrial Chemistry; Wiley-VCH: Weinheim, 2000.
(2) Leuckart, R. J. Prakt. Chem. 1890, 41, 179.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–E