Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
6
7
Goggiamani, L. M. Parisi, R. Bernini, J.DOOrI:g1.0C.1h03e9m/C.,52C0C00498, 3609K,
5608; (b) N. Umierski, G. Manolikakes, Org. Lett., 2013, 15,
188.
For selected examples, see: (a) X. D. Tang, L. B. Huang, C. R.
Qi, X. Wu, W. Q. Wu, H. F. Jiang, Chem. Commun., 2013, 49,
6102; (b) W. X. Zhang, J. Y. Xie, B. Rao, M. M. Luo, J. Org.
Chem., 2015, 80, 3504.
8
9
For selected examples, see: (a) P. Qu, C. Sun, J. Ma, F. Li, Adv.
Synth. Catal., 2014, 356, 447; (b) S.‐Y. Moon, J. Nam, K.
Rathwell, W.‐S. Kim, Org. Lett., 2014, 16, 338.
J. R. DeBergh, N. Niljianskul, S. L. Buchwald, J. Am. Chem.
Soc., 2013, 135, 10638
10 R. J. Cremlyn, Chlorosulfonic Acid: A Versatile Reagent; Royal
Society of Chemistry: Cambridge, 2002, pp. 7−21.
11 (a) B. Nguyen, E. J. Emmet, M. C. Willis, J. Am. Chem. Soc.,
2010, 132, 16372; (b) C. S. Richards‐Taylor, D. C. Blakemore,
M. C. Willis, Chem. Sci., 2014, 5, 222.
Scheme 5. Proposed mechanism.
12 For selected examples, see: (a) S. Ye, J. Wu, Chem. Commun.,
2012, 48, 7753; (b) S. Ye, J. Wu, Chem. Commun., 2012, 48,
10037; (c) D. Q. Zheng, Y. Y. An, Z. H. Li, J. Wu, Angew. Chem.,
Int. Ed., 2014, 53, 2451; (d) Y. Luo, X. Pan, C. Chen, L. Yao, J.
Wu, Chem. Commun., 2015, 51, 180; (e) X. Wang, L. Xue, Z.
Wang, Org. Lett., 2014, 16, 4056; (f) W. Li, H. Li, P. Langer, M.
Beller, X. Wu, Eur. J. Org. Chem., 2014, 3101.
B
and intermediate
single electron transfer to Fe3+ occurs immediately in
and regenerates Fe2+. Finally, the coupling between aryl
E
. Subsequently, another intramolecular
E
to form
C
∙‐
radical and SO2 , which are in‐situ generated from
though the same way as in path a, affords the corresponding
arylsulfinates.
B and C
13 (a) G.‐W. Wang, T. Miao, Chem. Eur. J., 2011, 17, 5787; (b) B.
Rao, W. Zhang, L. Hu, M. Luo, Green Chem., 2012, 14, 3436;
(c) X. Zeng, L. Ilies, E. Nakamura, J. Am. Chem. Soc.,
2011, 133, 17638; (d) H. Rao, L. Yang, Q. Shuai, C.‐J. Li, Adv.
Synth. Catal., 2011, 353 , 1701.
14 G. Pelzer, W. Keim, J. Mol. Catal. A, 1999, 139, 235.
15 A. Shavnya, S. B. Coffey, A. C. Smith, V. Mascitti, Org. Lett.,
2013, 15, 6226.
In summary, we have designed and successfully developed
the first iron‐catalyzd methodology for the installation of
sulfonyl unit into arenes. The important feature of this novel
strategy is furnishing arylsulfinates though very efficient
radical coupling reaction which is accomplished via iron‐
catalyzed reaction between readily available rongalite and
diaryliodoniums salts. The reaction proceeds fast at room
temperature to afford a number of arylsulfinates in modest to
excellent yields under air without the need of any ligands and
additives. The importance of the sulfonyl scaffold would
render this protocol attractive for both synthetic and medicinal
chemistry. Meanwhile, the reaction mechanism is proposed.
The utilization of other aryl radical precursors in this novel
radical coupling approach is undergoing.
16 E. J. Emmett, B. R. Hayter, M. C. Willis, Angew. Chem., Int.
Ed., 2014 , 53, 10204.
17 (a) M. W. Johnson, S. W. Bagley, N. P. Mankad, R. G.
Bergman, V. Mascitti, F. D. Toste, Angew. Chem., Int. Ed.,
2014, 53, 4404. (b) A. S. Deeming, C. J. Russell, M.C. Willis,
Angew. Chem., Int. Ed., DOI: 10.1002/anie.201508370
18 (a) C. Bolm, J. Legros, J. L. Paih, L. Zani, Chem. Rev., 2004, 104,
6217; (b) B. D. Sherry, A. Fürstner, Acc. Chem. Res., 2008, 41,
11, 1500.
19 (a) Z. Li, L. Cao, C.‐J. Li, Angew. Chem., Int. Ed. 2007, 46, 6505;
(b) W.‐T. Wei, M.‐B. Zhou, J.‐H. Fan, W. Liu, R.‐J. Song, Y. Liu,
M. Hu, P. Xie, J.‐H. Li, Angew. Chem., Int. Ed., 2013, 52, 3638;
(c) H.‐R. Wu, H.‐Y Huang, C.‐L. Ren, L. Liu, D. Wang, C.‐J. Li,
Chem. Eur. J., 2015, 21, 16744.
We gratefully acknowledge the National Natural Science
Foundation
of
China
(21321061,
21072134
and
J1103315/J0104) for financial support, and the Comprehensive
Training Platform of Specialized Laboratory, College of
Chemistry, Sichuan University for NMR and MS measurements.
20 (a) W. Du, L. Tian, J. Lai, X. Huo, X. Xie, X. She, S. Tang, Org.
Lett., 2014, 16, 2470; (b) L. Lv, H. Xi, X. Bai, Z. Li, Org. Lett.,
2015, 17, 4324.
21 M. Z. Lu, T. P. L, Org. Lett., 2014, 16, 4698.
22 (a) J. Xuan, T.‐T. Zeng, Z.‐J. Feng, Q.‐H. Deng, J.‐R. Chen, L.‐Q.
Lu, W.‐J. Xiao, H. Alper, Angew. Chem., Int. Ed., 2015, 54,
1625; (b) J. Ke, Y. Tang, H. Yi, Y. Li, Y. Cheng, C. Liu, A. Lei,
Angew. Chem., Int. Ed., 2015, 54, 6604; (c) J. L. Jeffrey, F. R.
Petronijevic, D. W. C. MacMillan, J. Am. Chem. Soc.,
2015, 137, 8404.
23 (a) C. Wakselman, M. Tordeux, J.‐L. Clavel, B. J. Langlois,
Chem. Soc., Chem. Commun., 1991, 993; (b) B.‐N. Huang, F.‐
H. Wu, C.‐M. Zhou J. Fluor. Chem., 1995, 75, 1; (c) S. Kotha, P.
Khedkar, Chem. Rev., 2012, 112, 1650
24 (a) J. Wen, R. Zhang, S. Chen, J. Li, J. Zhang, X. Yu, J. Org.
Chem., 2012, 77, 766; (b) J. Xu, P. Zhang, Y. Gao, Y. Chen, G.
Tang, Y. Zhao, J. Org. Chem., 2013, 78, 8176.
25 A. Baralle, L. Fensterbank, J. Goddard, C. Ollivier, Chem. Eur.
J., 2013, 19, 10809.
Notes and references
1
D. A. Smith, R. M. Jones, Curr. Opin. Drug Discovery Dev.,
2008, 11, 72.
R. Ettari, E. Nizi, M. E. Di Francesco, M.‐A. Dude, G. Pradel, R.
Vicik, T. Schirmeister, N. Micale, S. Grasso, M. Zappala, J.
Med. Chem., 2008, 51, 988.
2
3
4
(a) J. Drew, Science, 2000, 287, 1960; (b) P. Tfelt‐Hansen, P. D.
Vries, P. R. Saxena, Drugs, 2000, 60, 1259;
For selected examples, see: (a) K. Schank, The Chemistry of
Sulfones and Sulfoxides, Wiley, New York, 1988, Chapter 7; (b)
D. Antonow, T. Marrafa, I. Dawood, T. Ahmed, M. R. Haque,
D. E. Thurston, G. Zinzalla, Chem. Commun., 2010, 46, 2289.
For selected examples, see: (a) D. Baranano, J. F. Hartwig, J.
Am. Chem. Soc., 1995 , 117, 2937; (b) V. P. Reddy, A. V.
Kumar, K. Swapna, K. R. Rao, Org. Lett., 2009, 11, 1697.
5
26 D. H. R. Barton, J.‐P. Finet, C. Giannotti, F. Halley, J. Chem.
Soc., Perkin Trans. 1, 1987, 241‐249.
4 | J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins