COMMUNICATIONSCopper-Catalyzed Sulfenylation of Boronic Acids with Sulfonyl Hydrazides
2,2’-bipyridine (3.2 mg, 10 mol%) in 1,2-dichloroethane
(0.30 mL) was heated under air in a sealed tube at 1208C
(oil bath) for 15 h. The mixture was cooled to room temper-
ature and purified by silica gel chromatography (ethyl ace-
tate/petroleum ether, 0:1~1:4) to give thioether 3.
Angew. Chem. 2013, 125, 3541–3544; Angew. Chem.
Int. Ed. 2013, 52, 3457–3460.
[10] a) C. Chen, Y. Xie, L. Chu, R.-W. Wang, X. Zhang, F.-
L. Qing, Angew. Chem. 2012, 124, 2542–2545; Angew.
Chem. Int. Ed. 2012, 51, 2492–2495; b) L. Zhai, Y. Li, J.
Yin, K. Jin, R. Zhang, X. Fu, C. Duan, Tetrahedron
2013, 69, 10262–10266.
[11] F.-L. Yang, S.-K. Tian, Angew. Chem. 2013, 125, 5029–
5032; Angew. Chem. Int. Ed. 2013, 52, 4929–4932.
[12] a) R. Singh, D. S. Raghuvanshi, K. N. Singh, Org. Lett.
2013, 15, 4202–4205; b) N. Singh, R. Singh, D. S. Ra-
ghuvanshi, K. N. Singh, Org. Lett. 2013, 15, 5874–5877.
[13] X. Li, Y. Xu, W. Wu, C. Jiang, C. Qi, H. Jiang, Chem.
Eur. J. 2014, 20, 7911–7915.
Acknowledgements
We are grateful for the financial support from the National
Natural Science Foundation of China (21472178 and
21232007) and the National Key Basic Research Program of
China (2014CB931800).
[14] S.-R. Guo, W.-M. He, J.-N. Xiang, Y.-Q. Yuan, Chem.
Commun. 2014, 50, 8578–8581.
[15] G. Kumaraswamy, R. Raju, Adv. Synth. Catal. 2014,
356, 2591–2598.
[16] X. Zhao, L. Zhang, T. Li, G. Liu, H. Wang, K. Lu,
Chem. Commun. 2014, 50, 13121–13123.
[17] X. Kang, R. Yan, G. Yu, X. Pang, X. Liu, X. Li, L.
Xiang, G. Huang, J. Org. Chem. 2014, 79, 10605–10610.
[18] F.-L. Yang, F.-X. Wang, T.-T. Wang, Y.-J. Wang, S.-K.
Tian, Chem. Commun. 2014, 50, 2111–2113.
References
[1] For reviews, see: a) N. Miyaura, A. Suzuki, Chem. Rev.
1995, 95, 2457–2483; b) A. Suzuki, J. Organomet.
Chem. 1999, 576, 147–168; c) N. Miyaura, in: Metal-
Catalyzed Cross-Coupling Reactions, 2nd edn., (Eds:
A. de Meijere, F. Diederich), Wiley-VCH, Weinheim,
2004, pp 41–123.
[2] a) P. S. Herradura, K. A. Pendola, R. K. Guy, Org. Lett.
2000, 2, 2019–2022; b) R. Das, D. Chakraborty, Tetrahe-
dron Lett. 2012, 53, 7023–7027; c) H.-J. Xu, Y.-Q. Zhao,
T. Feng, Y.-S. Feng, J. Org. Chem. 2012, 77, 2878–2884.
[3] a) N. Taniguchi, Synlett 2006, 1351–1354; b) N. Tanigu-
chi, J. Org. Chem. 2007, 72, 1241–1245; c) J. Krouzelka,
I. Linhart, Eur. J. Org. Chem. 2009, 6336–6340; d) P.-S.
Luo, F. Wang, J.-H. Li, R.-Y. Tang, P. Zhong, Synthesis
2009, 921–928; e) A. Kumar, S. Kumar, Tetrahedron
2014, 70, 1763–1772.
[4] a) C. Savarin, J. Srogl, L. S. Liebeskind, Org. Lett. 2002,
4, 4309–4312; b) R. Pluta, P. Nikolaienko, M. Rueping,
Angew. Chem. 2014, 126, 1676–1679; Angew. Chem.
Int. Ed. 2014, 53, 1650–1653.
[5] a) A. K. Bakkestuen, L.-L. Gundersen, Tetrahedron
Lett. 2003, 44, 3359–3362; b) A. Lengar, C. O. Kappe,
Org. Lett. 2004, 6, 771–774; c) H. Prokopcovꢂ, C. O.
Kappe, Adv. Synth. Catal. 2007, 349, 448–452; d) H.
Prokopcovꢂ, C. O. Kappe, J. Org. Chem. 2007, 72,
4440–4448.
[6] a) J. M. Villalobos, J. Srogl, L. S. Liebeskind, J. Am.
Chem. Soc. 2007, 129, 15734–15735; b) A. Henke, J.
Srogl, Chem. Commun. 2011, 47, 4282–4284.
[19] a) F.-L. Yang, X.-T. Ma, S.-K. Tian, Chem. Eur. J. 2012,
18, 1582–1585; b) Y.-H. Su, Z. Wu, S.-K. Tian, Chem.
Commun. 2013, 49, 6528–6530; c) T.-T. Wang, F.-X.
Wang, F.-L. Yang, S.-K. Tian, Chem. Commun. 2014,
50, 3802–3805; d) Y.-G. Zhang, X.-L. Liu, Z.-Y. He, X.-
M. Li, H.-J. Kang, S.-K. Tian, Chem. Eur. J. 2014, 20,
2765–2769; e) Y. Wang, J.-K. Xu, Y. Gu, S.-K. Tian,
Org. Chem. Front. 2014, 1, 812–816.
[20] During our investigation, the reaction of arylboronic
acids with arylsulfonyl hydrazides in the presence of
1.5 equiv of Cu(OAc)2 has been reported to give diaryl
sulfones. See: X.-M. Wu, Y. Wang, Synlett 2014, 25,
1163–1167. However, in our case no sulfone product
was isolated.
[21] A. Deavin, C. W. Rees, J. Chem. Soc. 1961, 4970–4973.
[22] Cu(I)/Cu(III) catalytic cycles were proposed by Jiang
and Taniguchi in the copper(I) salt-catalyzed sulfenyla-
tion of aromatic compounds with thiosulfonates
(ref.[13]) and sulfenylation of boronic acids with disul-
fides (ref.[3b]), respectively.
[23] a) Q. Lu, J. Zhang, F. Wei, Y. Qi, H. Wang, Z. Liu, A.
Lei, Angew. Chem. 2013, 125, 7297–7300; Angew.
Chem. Int. Ed. 2013, 52, 7156–7159; b) Q. Lu, J. Zhang,
G. Zhao, Y. Qi, H. Wang, A. Lei, J. Am. Chem. Soc.
2013, 135, 11481–11484; c) S. Tang, Y. Wu, W. Liao, R.
Bai, C. Liu, A. Lei, Chem. Commun. 2014, 50, 4496–
4499; d) J. Yuan, X. Ma, H. Yi, C. Liu, A. Lei, Chem.
Commun. 2014, 50, 14386–14389.
[7] N. Sun, H. Zhang, W. Mo, B. Hu, Z. Shen, X. Hu, Syn-
lett 2013, 24, 1443–1447.
[8] L. Wang, W.-Y. Zhou, S.-C. Chen, M.-Y. He, Q. Chen,
Synlett 2011, 3041–3045.
[9] a) C.-P. Zhang, D. Vicic, Chem. Asian J. 2012, 7, 1756–
1758; b) X. Shao, X. Wang, T. Yang, L. Lu, Q. Shen,
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5
ÞÞ
These are not the final page numbers!